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| United States Patent |
6,165,704
|
|
Miyake
, et al.
|
December 26, 2000
|
Silver halide photographic light-sensitive material
Abstract
There is disclosed a silver halide photographic light-sensitive material
which contains, on a support, a specific nitrogen-containing heterocyclic
compound, and a divalent metal cation that is an acid with intermediate
hardness/softness classified in accordance with the HSAB principle, in an
amount 1 to 300 times the number of moles of the nitrogen-containing
heterocyclic compound. The light-sensitive material can form an image with
high sensitivity and low fogging, both in heat-development processing
characterized by its ease and rapidness, and in usual liquid-developing
processing that is widely used.
| Inventors:
|
Miyake; Kiyoteru (Minami-ashigara, JP);
Ikeda; Tadashi (Minami-ashigara, JP)
|
| Assignee:
|
Fuji Photo Film Co., Ltd. (Minami-ashigara, JP)
|
| Appl. No.:
|
396463 |
| Filed:
|
September 15, 1999 |
Foreign Application Priority Data
| Sep 16, 1998[JP] | 10-280598 |
| Current U.S. Class: |
430/600; 430/405; 430/448; 430/566; 430/604; 430/608; 430/613 |
| Intern'l Class: |
G03C 001/09; G03C 001/34 |
| Field of Search: |
430/550,551,600,604,608,613
|
References Cited
U.S. Patent Documents
| 5194362 | Mar., 1993 | Nakabayashi et al. | 430/203.
|
| 5223384 | Jun., 1993 | Ohbayashi et al. | 430/203.
|
| 5908736 | Jun., 1999 | Yamazaki | 430/203.
|
| 6001543 | Dec., 1999 | Asami et al. | 430/551.
|
| Foreign Patent Documents |
| 8-54705 | Feb., 1996 | JP.
| |
| 8-54724 | Feb., 1996 | JP.
| |
Primary Examiner: Le; Hoa Van
Attorney, Agent or Firm: Burns, Doane, Swecker & Mathis, LLP
Claims
What we claim is:
1. A silver halide photographic light-sensitive material, which contains,
in a silver halide emulsion layer on a support, at least one
nitrogen-containing heterocyclic compound represented by one of general
formula (1), (2), (3), (4) or (5), a divalent metal cation that is an acid
with intermediate hardness/softness classified in accordance with the HSAB
principle, in an amount 1 to 300 times the number of moles of the
nitrogen-containing heterocyclic compound, and an anion acting as a
counter ion, the anion being selected from the group consisting of a
nitrate ion, a sulfate ion, a chloride ion, a bromide ion, an iodide ion,
a carbonate ion, a sulfite ion, a bicarbonate ion, a bisulfite ion, an
ammonium ion, an acetate ion and a phosphate ion, wherein the
nitrogen-containing heterocyclic compound and the divalent metal cation
are included in the same silver halide emulsion layer:
##STR27##
wherein R.sub.a, R.sub.b, R.sub.c, and R.sub.d each independently
represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl
group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy
group, an aryloxy group, an amino group, an acylamino group, a ureido
group, a urethane group, a sulfonamide group, a sulfamoyl group, a
carbamoyl group, a sulfonyl group, an oxycarbonyl group, an acyl group, an
acyloxy group, an alkylthio group or an arylthio group, in which the
number of carbon atoms of the R.sub.a is 4 or more but 16 or less, the
total number of carbon atoms of the R.sub.b is 10 or more, and the sum of
carbon atoms of R.sub.c and R.sub.d is 12 or more; each of T represent a
nitrogen atom, C--H or C--SH; each of U represent a nitrogen atom, C--H,
C--SH or C--R.sub.a, and at least one of them is C--R.sub.a ; each of X
represent a nitrogen atom or C--H; Y represents an oxygen atom, a sulfur
atom, or N--H;
M, if it is univalent, represents a hydrogen atom, an alkali metal atom, a
quaternary ammonium group, or a quaternary phosphonium group, with n being
1; M, if it is divalent, represents an alkaline earth metal atom, a
cadmium, or an atom being a divalent metal cation having intermediate
hardness/softness in accordance with the HSAB principle, with n being 2;
M, if it is trivalent, represents a boron, an aluminum, or an iron, with n
being 3; in general formulae (1) and (2), the benzene ring may have a
substituent.
2. The silver halide photographic light-sensitive material as claimed in
claim 1, which has, on a support, a photosensitive layer comprising a
silver halide emulsion that contains silver halide tabular grains with a
thickness of 0.2 .mu.m or less.
3. The silver halide photographic light-sensitive material as claimed in
claim 1, which has, on a support, a photosensitive layer comprising a
silver halide emulsion that contains silver halide in which silver
chloride content is 50 mol % or more.
4. The silver halide photographic light-sensitive material as claimed in
claim 1, wherein the divalent metal cation is a zinc ion, a copper ion, a
nickel ion, or a lead ion.
5. The silver halide photographic light-sensitive material as claimed in
claim 4, wherein the divalent metal cation is a zinc ion.
6. The silver halide photographic light-sensitive material as claimed in
claim 1, which contains a developing agent represented by any one of
general formulae (6) to (9)
##STR28##
wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl
group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group,
an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an
aryloxy group, an alkylthio group, an arylthio group, an alkylcarbamoyl
group, an arylcarbamoyl group, a carbamoyl group, an alkylsulfamoyl group,
an arylsulfamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl
group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl
group, an alkylcarbonyl group, an arylcarbonyl group, or an acyloxy group;
R.sub.5 represents an alkyl group, an aryl group, or a heterocyclic group;
Z represents a group of atoms forming a (hetero)aromatic ring, if z is a
benzene ring, the sum of Hammett's constant (.sigma.) of its substituents
is 1 or more; R.sub.6 represents an alkyl group; X represents an oxygen
atom, a sulfur atom, a selenium atom, or an alkyl- or aryl-substituted
tertiary nitrogen atom; R.sub.7 and R.sub.8 represent a hydrogen atom or a
substituent, or R.sub.7 and R.sub.8 may bond together to form a double
bond or a ring; and at least one ballasting group having 8 or more carbon
atoms is contained in each of general formulae (6) to (9), in order to
impart oil-solubility to the molecule thereof.
7. The silver halide photographic light-sensitive material as claimed in
claim 1, wherein an image can be formed by:
a development by heat, wherein water, whose amount corresponds to from 1/10
of to 1-fold times the volume of water required for the maximum swelling
of an entire coated film of the light-sensitive material, is made to lie
between the light-sensitive material and a processing material that
contains a base and/or a base precursor, and these materials are processed
with overlapping each other, or
a development using a processing bath containing a developing agent that is
an aromatic primary amine.
8. The silver halide photographic light-sensitive material as claimed in
claim 1, wherein the amount of the divalent metal cation to be added is
1.5 to 200 times the number of moles of the nitrogen-containing
heterocyclic compound.
9. The silver halide photographic light-sensitive material as claimed in
claim 1, wherein the amount of the divalent metal cation to be added is
3.times.10.sup.-3 to 1 mol per mol of silver.
10. The silver halide photographic light-sensitive material as claimed in
claim 1, wherein the amount of the divalent metal cation to be added is
30% or less of the total amount of gelatin in the same layer.
11. The silver halide photographic light-sensitive material as claimed in
claim 1, wherein the amount of the compound represented by any one of
formulae (1) to (5) to be added is 10.sup.-5 to 1 mole per mole of the
silver halide, when the compound is added to a silver halide emulsion
layer.
12. The silver halide photographic light-sensitive material as claimed in
claim 1, which contains, as the compound, a compound represented by
general formula (1) or (2) having no mercapto group, and a compound
selected from a compound represented by general formula (1) or (2) having
a mercapto group or a compound represented by any one of general formulae
(3) to (5).
Description
FIELD OF THE INVENTION
The present invention relates to a silver halide photographic
light-sensitive material for photography. More specifically, the present
invention relates to a light-sensitive material that can form an image
with high sensitivity and low fogging easily and rapidly, both in
heat-development processing and in liquid development processing that uses
a bath containing a developing agent.
BACKGROUND OF THE INVENTION
Hitherto, a photographic process in which silver halides are used has been
most widely used as it is excellent in photographic characteristics, such
as sensitivity, gradation adjustment, resolving power, and the like, in
comparison with other methods, such as electrophotography or diazo
photography. The process is still being developed further, and currently
it is possible to easily obtain a black-and-white image or color image
with high image quality.
However, there is an increasingly strong demand for a process to obtain a
photographed image more simply and rapidly, with a low environmental load.
To attempt easier processing, a heat-developable color light-sensitive
material for photographing containing therein a developing agent, is
disclosed in JP-A-9-274295 ("JP-A" means unexamined published Japanese
patent application). In heat-developing system, in general, though an
image can be rapidly formed, fogging occurs readily, and attainment of
good discrimination is not easy. JP-A-10-90848 discloses that, with
respect to fog in a heat-developable light-sensitive material, not only
emulsion fog but also development fog (heat fog) due to high-temperature
processing contributes largely, and that, in order to restrain the heat
fog and to achieve both high sensitivity and good discrimination of
images, a specific antifogging agent is useful.
In fact that the above-mentioned antifogging agent, when used in
heat-development, performs a maximum discrimination effect; however, when
used in color-development process employing a currently available
developing agent of paraphenylenediamine, there is a problem that it has
strong desensitization effects, causing low sensitivity and/or low
density. Therefore, such a light-sensitive material is unfit as a
heat-developable light-sensitive material for photographing.
If a light-sensitive material for heat-development has compatibility with a
conventional processing used in a widely-prevailing, small-sized, and
simple printer processor, the so-called "mini-lab", installed in
laboratories for color photography or stores, it can make conventional
processing possible, as well as rapid processing, not requiring special
additional equipment, to allow anyone to easily enjoy color photography.
Such a heat-developable light-sensitive material that can be also used in
conventional color-developing processing has long been desired.
SUMMARY OF THE INVENTION
A primary object of the present invention is to provide a light-sensitive
material having characteristics of high sensitivity and low fogging, which
can be used both in heat-development processing characterized by its ease
and rapidness, and in conventional liquid-developing processing that is
widely used.
Other and further objects, features, and advantages of the invention will
appear more fully from the following description.
DETAILED DESCRIPTION OF THE INVENTION
The object of the present invention can be attained by a light-sensitive
material described in the following items (1) to (6).
(1) A silver halide photographic light-sensitive material, which contains,
on a support, at least one nitrogen-containing heterocyclic compounds
represented by one of general formula (1), (2), (3), (4) or (5), and
contains a divalent metal cation that is an acid with intermediate
hardness/softness classified in accordance with the HSAB principle, in an
amount 1 to 300 times the number of moles of the nitrogen-containing
heterocyclic compound:
##STR1##
wherein R.sub.a, R.sub.b, R.sub.c, and R.sub.d each independently
represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl
group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy
group, an aryloxy group, an amino group, an acylamino group, a ureido
group, a urethane group, a sulfonamide group, a sulfamoyl group, a
carbamoyl group, a sulfonyl group, an oxycarbonyl group, an acyl group, an
acyloxy group, an alkylthio group or an arylthio group, in which the
number of carbon atoms of the R.sub.a is 4 or more but 16 or less, the
total number of carbon atoms of the R.sub.b is 10 or more, and the sum of
carbon atoms of R.sub.c and R.sub.d is 12 or more; each of T represent a
nitrogen atom, C--H or C--SH; each of U represent a nitrogen atom, C--H,
C--SH or C--R.sub.a, and at least one of them is C--R.sub.a ; each of X
represent a nitrogen atom or C--H; Y represents an oxygen atom, a sulfur
atom, or N--H;
M, if it is univalent, represents a hydrogen atom, an alkali metal atom, a
quaternary ammonium group, or a quaternary phosphonium group, with n being
1; M, if it is divalent, represents an alkaline earth metal atom, a
cadmium, or an atom being a divalent metal cation having intermediate
hardness/softness in accordance with the HSAB principle, with n being 2;
M, if it is trivalent, represents a boron, an aluminum, or an iron, with n
being 3; in general formulae (1) and (2), the benzene ring may have a
substituent.
(2) The silver halide photographic light-sensitive material described in
the above item (1), which has, on a support, a photosensitive layer
comprising a silver halide emulsion that contains tabular silver halide
grains with a thickness of 0.2 .mu.m or less.
(3) The silver halide photographic light-sensitive material described in
the above item (1) or (2), wherein it comprises, on a support, a
photosensitive layer comprising a silver halide emulsion that contains
silver halide in which silver chloride content is 50 mol % or more.
(4) The silver halide photographic light-sensitive material described in
the above items (1), (2), or (3), wherein the divalent metal cation is a
zinc ion, a copper ion, a nickel ion, or a lead ion.
(5) The silver halide photographic light-sensitive material described in
any one of the above items (1) to (4), wherein it contains a developing
agent represented by any one of general formulae (6) to (9).
##STR2##
wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each independently
represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl
group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group,
an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an
aryloxy group, an alkylthio group, an arylthio group, an alkylcarbamoyl
group, an arylcarbamoyl group, a carbamoyl group, an alkylsulfamoyl group,
an arylsulfamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl
group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl
group, an alkylcarbonyl group, an arylcarbonyl group, or an acyloxy group;
R.sub.5 represents an alkyl group, an aryl group, or a heterocyclic group;
Z represents a group of atoms forming a (hetero)aromatic ring, if Z is a
benzene ring, the sum of Hammett's constant (.sigma.) of its substituents
is 1 or more; R.sub.6 represents an alkyl group; X represents an oxygen
atom, a sulfur atom, a selenium atom, or an alkyl- or aryl-substituted
tertiary nitrogen atom; R.sub.7 and R.sub.8 each represent a hydrogen atom
or a substituent, or R.sub.7 and R.sub.8 may bond together to form a
double bond or a ring; further, at least one ballasting group having 8 or
more carbon atoms is contained in each of general formulae (6) to (9), in
order to impart oil-solubility to the molecule.
(6) The silver halide photographic light-sensitive material described in
any one of the above items (1) to (5), wherein an image can be formed by:
a development by heat, wherein water, whose amount corresponds to 1/10 to
1-fold times the volume of water required for the maximum swelling of an
entire coated film of the light-sensitive material, is made to lie between
the light-sensitive material and a processing material that includes a
base and/or a base precursor, and these materials are processed with
overlapping each other, or
a development using a processing bath containing a developing agent that is
an aromatic primary amine.
The divalent metal cation used in the present invention, which is an acid
having intermediate hardness/softness in accordance with HSAB principle,
is hereinafter described.
As the acid used in the present invention is classified to the intermediate
portion on a scale according to HSAB principle, it can be said it has
intermediate hardness or intermediate softness.
The HSAB principle (Principle of Hard and Soft Acids and Bases) is a
principle proposed by R. G. Pearson to classify the strength of acids and
bases in view of "hardness" or "softness". A hard acid has strong affinity
to a hard base, while a soft acid has strong affinity to a soft base.
A "hard acid" is an acid having a small atom that acts as an electron
acceptor, having no valence electron entered into an orbit that is easily
deformed, and having a high positive charge. A "soft acid" is an acid
having a large atom that acts as an electron acceptor, having valence
electrons entered in an orbit that is easily deformed, and carrying no or
little electrical charge.
A "hard base" is one in which a valence electron binds strongly to an atom.
A "soft base" is one in which a valence electron is readily polarized.
The HSAB principle and classification of acids and bases based on the
principle are described in Section 15 of Chapter 9 in "Inorganic
Chemistry--A Guide to Advanced Study" by R. B. Heslop and K. Jones.
Examples of the divalent metal cation being an acid having intermediate
hardness/softness in accordance with the HSAB principle include an iron
ion, a copper ion, a zinc ion, a nickel ion, a lead ion, a cobalt ion and
a tin ion, with preference given to an iron ion, a zinc ion, a nickel ion,
a lead ion, and cobalt ion. Two or more kind of ions out of them may be
used at the same time. Particularly, the zinc ion, nickel ion, and lead
ion are preferably used. A zinc ion is especially preferable.
The divalent metal cation, being an acid having intermediate
hardness/softness according to the HSAB principle, reacts with a
nitrogen-containing heterocyclic compound, to stably form a complex
thereof, and it is presumed that this reaction serves to achieve an effect
of the present invention.
Examples of anions acting as a counter ion include a nitrate ion, a sulfate
ion, a chloride ion, a bromide ion, an iodide ion, a carbonate ion, a
sulfite ion, a bicarbonate ion, a bisulfite ion, an ammonium ion, an
acetate ion, a phosphate ion or the like. Preferably, a nitrate ion, a
sulfate acid ion, a chloride ion, a bromide ion, and an acetate ion are
used, because they have less photographic effects. The nitrate ion is
particularly preferably used.
A water-soluble compound is preferably used as a compound containing
divalent ions for use in the present invention. For example, zinc nitrate
hexahydrate, nickel nitrate, copper sulfate hexahydrate, zinc sulfate,
lead acetate trihydrate, ferrous sulfate, cobaltous nitrate are used.
The divalent metal cation used in the present invention can be added to any
of a silver halide emulsion layer, an intermediate layer, a protective
layer, a subbing layer, and an antihalation layer; and, it is preferable
to add the metal cation to a layer to which a nitrogen-containing
heterocyclic compound, described later, is added.
As to timing of their addition, these divalent metal cations may be added
either before or after the addition of the nitrogen-containing
heterocyclic compound.
According to the present invention, the time interval between the addition
of the divalent metal cation and the nitrogen-containing heterocyclic
compound is preferably 90 minutes or less, more preferably 45 minutes or
less, and further preferably 20 minutes or less.
Preferably, these compounds are added in the presence of gelatin or other
water-soluble binders.
If the nitrogen-containing heterocyclic compound is added to oil in a
gelatin dispersion of a coupler, the divalent metal cation may be added to
the gelatin.
A gelatin dispersion prepared by adding the nitrogen-containing
heterocyclic compound to a gelatin solution containing the divalent metal
cation may be used as well.
The addition amount of the divalent metal cation to a light-sensitive
material is preferably 1 to 300 times, in terms of moles, the sum of total
amount of the below-mentioned nitrogen-containing heterocyclic compound
for each layer, more preferably 1.5 to 200 times, and particularly
preferably 2 to 100 times.
The divalent metal cation reacted with the nitrogen-containing heterocyclic
compound to form a complex is not deemed to be a component of heterocyclic
compound and is considered to be an "added" cation, in the present
invention.
The amount of the divalent metal cation per mol of silver is preferably
3.times.10.sup.-3 to 1 mol, more preferably 5.times.10.sup.-3 to
5.times.10.sup.-1 mol, and further preferably 10.sup.-2 to 10.sup.-1 mol.
Since viscosity increases due to the reaction between the divalent metal
cation and the gelatin, the amount of the divalent metal cation to be
added is preferably 30% or less of the total amount of the gelatin in the
added layer, and more preferably 20% or less, by weight.
If excessive divalent metal cations exist concomitantly with the
nitrogen-containing heterocyclic compound, various complexes, each having
a large mole ratio of a divalent metal salt or a divalent metal ion, are
produced. However, the complex would not become coarse to cause
precipitation, and it is suspended almost uniformly, under the presence of
the gelatin and/or the binder.
Also, in the present invention, the divalent metal cation exists in excess,
compared with the divalent metal salt of formulae (1) to (5), and thus the
metal salt is stabilized. If a divalent metal ion exists only as a
divalent metal salt of a nitrogen-containing heterocyclic compound, as
described in U.S. Pat. No. 3,649,267, JP-A-62-291642, JP-A-8-54705, and
JP-A-8-54724, the metal salt is unstable, and therefore the
nitrogen-containing heterocyclic compound is liberated, to be adsorbed to
silver halide particles, resulting in great desensitization in usual
color-developing treatment. Therefore, such addition does not exhibit the
effect desired in the present invention.
Because of the presence of excessive amounts of the divalent metal cations,
the divalent metal salt produced in accordance with the present invention
is not sparingly soluble, differing from those disclosed in JP-A-8-54705
and JP-A-8-54724.
JP-A-10-161263 and JP-A-10-161262 describe that a zinc ion, if added to a
gelatin dispersion of an emulsion when a metal cyanic complex is doped in
a silver halide, serves to suppress the inhibition of gold sensitization,
and is preferable in view of attaining high sensitivity. However, in these
publications, the amount of zinc to be added is 0.5 mole or less per mole
of the nitrogen-containing heterocyclic compound. This range of the amount
of zinc is different from that of the present invention, and it cannot
give the effect expected in the present invention.
Next, the nitrogen-containing heterocyclic compound used in the present
invention is described below.
The compounds represented by general formulae (1) and (2) are a
benzimidazole compound, a benzopyrazole compound, a benzotriazole
compound, or the like. The compound may have a mercapto group. In general
formulae (1) and (2), the benzene ring may have a substituent.
Each of T represents a nitrogen atom, C--H or C--SH. Each of U represents a
nitrogen atom, C--H, C--SH, or C--R.sub.a, and at least one of them is
C--R.sub.a.
R.sub.a is a substituted or unsubstituted group, having carbon atoms of 4
to 16, that includes an alkyl group (e.g., n-butyl, t-butyl, n-octyl,
dodecyl and hexadecyl), a cycloalkyl group (e.g., cyclopentyl and
cyclohexyl), an alkenyl group (e.g., 2-butenyl and 3-pentenyl), an alkynyl
group (e.g., 3-pentynyl), an aralkyl group (e.g., benzyl and phenethyl),
an aryl group (e.g., phenyl, naphthyl and 4-methylphenyl), a heterocyclic
group (e.g., pyridyl, furyl, imidazolyl, piperidinyl and morpholyl), an
alkoxy group (e.g., methoxy, ethoxy, butoxy, 2-ethylhexyloxy,
ethoxyethoxy, methoxyethoxy and dodecyloxy), an aryloxy group (e.g.,
phenoxy and 2-naphthyloxy), an amino group (e.g., diethylamino,
dipropylamino, dibutylamino, butylamino, dibenzylamino and anilino), an
acylamino group (e.g., benzoylamino, octanoylamino, 2-ethylhexanoylamino
and dodecanoylamino), a ureido group (e.g., N-butylureido, N-phenylureido,
hexylureido, octylureido and dodecylureido), a thioureido group (e.g.,
N-butylthioureido, N-phenylthioureido and octylthioureido), a urethane
group (e.g., butoxycarbonylamino, phenoxycarbonylamino and
hexyloxycarbonylamino), a sulfonamido group (e.g., butanesulfonamido,
benzenesulfonamido and octanesulfonamido), a sulfamoyl group (e.g.,
N,N-propylsulfamoyl, N-phenylsulfamoyl and dibutylsulfamoyl), a carbamoyl
group (e.g., N,N-dipropylcarbamoyl, N-phenylcarbamoyl, octylcarbamoyl, and
dodecylcarbamoyl), a sulfonyl group (e.g., tosyl), a sulfinyl group (e.g.,
butylsulfinyl and phenylsulfinyl), an oxycarbonyl group (e.g.,
butoxycarbonyl, naphthoxycarbonyl, hexyloxycarbonyl and phenoxycarbonyl),
an acyl group (e.g., benzoyl and octanoyl), an acyloxy group (e.g.,
benzoyloxy and octanoyloxy), a phosphoric acid amide group (e.g.
N,N-dipropylphosphoric amide), an alkylthio group (e.g., butylthio,
pentylthio, hexylthio and decylthio), an arylthio group (e.g.,
phenylthio), or the like. As examples of the substituents, those explained
in R.sub.a, a hydroxyl group, a halogen group (e.g., fluorine, chlorine,
bromine or iodine), an amino group, a nitro group, a cyano group, a
sulfonic group, a carboxyl group, a methyl group, an ethyl group, a propyl
group, an isopropyl group, or the like can be mentioned.
Examples of the substituent for the benzene ring include a hydroxyl group,
a halogen group (e.g., fluorine, chlorine, bromine or iodine), an amino
group, a nitro group, a cyano group, a sulfonic group, a carboxyl group, a
methyl group, an ethyl group, a propyl group, an isopropyl group, or the
like.
Preferably, R.sub.a is a substituted or unsubstituted group having 6 or
more and 12 or less carbon atoms, including an acylamino group, a ureido
group, a urethane group, a sulfonamido group, a carbamoyl group, or an
oxycarbonyl group, and most preferably, R.sub.a is a substituted or
unsubstituted group having 6 or more but 12 or less carbon atoms,
including an acylamino group, a ureido group, and an carbamoyl group.
M is preferably a hydrogen atom, an alkali metal atom, an alkaline earth
metal atom, a nickel atom, a zinc atom, a cadmium atom, an iron atom, or a
lead atom, more preferably a zinc atom, a calcium atom, or a cadmium atom,
and particularly preferably a zinc atom.
The compounds represented by general formulae (3) to (5) are a
mercaptotetrazole compound, a mercaptotriazole compound, a
mercaptoimidazole compound, a mercaptothiadiazole compound, a
mercaptooxadiazole compound, or the like.
Each of X represent a nitrogen atom or C--H. Y is an oxygen atom, or a
sulfur atom.
R.sub.b is a substituted or unsubstituted group including an alkyl group
(e.g., decyl, dodecyl and hexadecyl), a cycloalkyl group (e.g.,
butylcyclohexyl), an alkenyl group (e.g., 3-decenyl), an alkynyl group
(e.g., decynyl), an aralkyl group (e.g., 4-butylbenzyl and
3-propylphenethyl), an aryl group (e.g., 4-butylphenyl, and naphthyl), a
heterocyclic group (e.g., quinolyl, and quinoxalinyl), an alkoxy group
(e.g., dodecyloxy), an aryloxy group (e.g., 2-naphthyloxy), an amino group
(e.g., didecylamino, dipentylamino, and dibenzylamino), an acylamino group
(e.g., decylamino, 2-butylhexanoylamino, and dodecanoylamino), a ureido
group (e.g., N-naphthylureido, decylureido, and dodecylureido), a
thioureido group (e.g., N-naphthylthioureido, and decylthioureido), a
urethane group (e.g., naphthoxycarbonylamino, and decyloxycarbonylamino),
a sulfonamide group (e.g., decanesulfonamido, and naphthalenesulfonamido),
a sulfamoyl group (e.g., N,N-pentyloctylsulfamoyl, N-naphthylsulfamoyl,
and dipentylsulfamoyl), a carbamoyl group (e.g., N,N-dipentylcarbamoyl,
N,N-phenylbutylcarbamoyl, and dodecylcarbamoyl), a sulfonyl group (e.g.,
tosyl), a sulfinyl group (e.g., decylsulfinyl, and naphthylsulfinyl), an
oxycarbonyl group (e.g., decyloxycarbonyl, and naphthoxycarbonyl), an acyl
group (e.g., butylbenzoyl), an acyloxy group (e.g., penthylbenzoyloxy), an
phosphoric acid amido group (e.g., N,N-dipentylphosphoric amido), an
alkylthio group (e.g., decylthio), an arylthio group (e.g., naphthylthio),
or the like. These groups may be further substituted. Examples of the
substituents that further substitute include, substituents explained in
R.sub.b, a hydroxyl group, a halogen group (fluorine, chlorine, bromine,
and iodine), an amino group, a nitro group, a cyano group, a sulfonic
group, a carboxyl group, a methyl group, an ethyl group, a propyl group,
an isopropyl group, or the like.
The total number of carbon atoms of R.sub.b is generally 10 or more.
R.sub.b is preferably a substituted group, including an aryl group (e.g.,
phenyl, naphthyl, and anthracenyl), an acylamino group, a ureido group, a
urethane group, a sulfonamide group, a carbamoyl group, and an oxycarbonyl
group. Examples of the substituted are a carbamoyl group having an alkyl
group such as a butyl, a hexyl, an octyl or a nonyl; an amido group having
the same alkyl group; a ureido group having the same alkyl group; an
alkylcarboxylic acid ester group, or the like. In addition to have 10 or
more carbon atoms in total, preferably, the five-membered ring has an
aromatic ring group that binds directly thereto.
M has the same meaning as in general formulae (1) and (2). That is,
preferably, M is a hydrogen atom, an alkali metal atom, an alkaline earth
metal atom, a nickel, a zinc, a cadmium, an iron, or a lead, more
preferably, a zinc, a calcium or a cadmium, and particularly preferably a
zinc.
R.sub.c and R.sub.d are each independently a substituted or unsubstituted
group, including an alkyl group (e.g., n-butyl, t-butyl, n-octyl, dodecyl,
and hexadecyl), a cycloalkyl group (e.g., cyclopentyl, and cyclohexyl), an
alkenyl group (e.g., allyl, 2-butenyl, and 3-pentenyl), an alkynyl group
(e.g., propargyl, and 3-pentynyl), an aralkyl group (e.g., benzyl, and
phenethyl), an aryl group (e.g., phenyl, naphthyl, and 4-methylphenyl), a
heterocyclic group (e.g., pyridyl, furyl, imidazolyl, piperidinyl,
morpholyl, and thienyl), an alkoxy group (e.g., methoxy, ethoxy, butoxy,
2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy, and dodecyloxy), an aryloxy
group (e.g., phenoxy, and 2-naphthyloxy), an amino group (e.g.,
unsubstituted amino, dimethylamino, diethylamino, dipropylamino,
dibutylamino, ethylamino, dibenzylamino, and anilino), an acylamino group
(e.g., acetylamino, benzoylamino, octanoylamino, 2-ethylhexanoylamino, and
dodecanoylamino), a ureido group (e.g., unsubstituted ureido,
N-methylureido, N-phenylureido, hexylureido, octylureido, and
dodecylureido), a thioureido group (e.g., unsubstituted thioureido,
N-methylthioureido, N-phenylthioureido, and octylthioureido), a urethane
group (e.g., methoxycarbonylamino, phenoxycarbonylamino, and
hexyloxycarbonylamino), a sulfonamido group (e.g., methanesulfonamido,
benzenesulfonamido, and octanesulfonamide), a sulfamoyl group (e.g.,
unsubstituted sulfamoyl group, N,N-dimethylsulfamoyl, N-phenylsulfamoyl,
and dibutylsulfamoyl), a carbamoyl group (e.g., unsubstituted carbamoyl,
N,N-diethylcarbamoyl, N-phenylcarbamoyl, octylcarbamoyl,
dodecylcarbamoyl), a sulfonyl group (e.g., mesyl, and tosyl), a sulfinyl
group (e.g., methylsulfinyl, and phenylsulfinyl), an oxycarbonyl group
(e.g., methoxycarbonyl, ethoxycarbonyl, hexyloxycarbonyl, and
phenoxycarbonyl), an acyl group (e.g., acetyl, benzoyl, formyl, pivaloyl,
and octanoyl), an acyloxy group (e.g., acetoxy, benzoyloxy, and
octanoyloxy), an phosphoric acid amido group (e.g., N,N-diethylphosphoric
amido), an alkylthio group (e.g., methylthio, ethylthio, hexylthio, and
decylthio), an arylthio group (e.g., phenylthio), a cyano group, a sulfo
group, a carboxy group, a hydroxy group, a phosphono group, a nitro group,
or the like. These groups may be further substituted. Examples of the
substituents for the further substitution are, those explained in R.sub.c
and R.sub.d, and a hydroxyl group, a halogen group (e.g., fluorine,
chlorine, bromine, and iodine), an amino group, a nitro group, a cyano
group, a sulfonic group, a carboxyl group, a methyl group, an ethyl group,
a propyl group, an isopropyl group, or the like.
R.sub.c and R.sub.d are each independently selected from a substituted or
unsubstituted alkyl group (e.g., butyl, hexyl, octyl, decyl, or the like),
a substituted or unsubstituted alkenyl group (e.g., butenyl, octenyl, or
the like), a substituted or unsubstituted aralkyl group (e.g., benzyl,
phenethyl, or the like), a substituted or unsubstituted aryl group (e.g.,
phenyl, biphenyl, amidophenyl, phenoxyphenyl, naphthyl, anthracenyl, or
the like), or a substituted or unsubstituted heterocyclic group (e.g.,
pyridyl, thienyl, furyl, or the like). Preferably, the sum of carbon atoms
of R.sub.c and R.sub.d is 12 or more, and in addition, they preferably
have an aromatic ring. Further, preferably, the aromatic ring group binds
directly to the five-membered ring.
To achieve high sensitivity and low Dmin, combined use of a compound
represented by general formula (1) or (2) having no mercapto group, and a
compound selected from a compound represented by general formula (1) or
(2) having a mercapto group or a compound represented by any one of
general formulae (3) to (5), is preferable. Combined use of a compound
represented by general formula (1) or (2) having no mercapto group, and a
compound represented by any one of general formulae (3) to (5), is more
preferable.
It is also preferable to use a nitrogen-containing heterocyclic compound
which has a partition coefficient for butanol and water at pH 11, a common
logarithm of which is 0.5 or more.
The partition coefficient of butanol to water can be obtained by the
following procedure. 50 cc of a n-butanol solution of 2.times.10.sup.-4
mol/l of a test compound was mixed with 50 cc of Britton-Robinson buffer
(pH 11) prepared using distilled water, at an ordinary temperature, the
resulting mixture was shaken with a shaker for 10 minutes and then left to
stand. Then, the solution was separated into the n-butanol phase (A
liquid) and the water phase (B liquid). The extracted A and B liquids were
diluted by n-butanol liquid and buffer liquid, respectively, at a certain
rate. The concentrations of both liquids were measured by a spectral
absorption measurement method or an HPLC method at a measurement
temperature of 25.degree. C. The common logarithm of the partition
coefficient was calculated from the concentration of each respective
liquid.
(Partition coefficient)=[Concentration in n-butanol phase]/[Concentration
in buffer phase]
These compounds are added to an emulsion layer in accordance with an
ordinary method for adding photographic emulsion additives. These
compounds can be added as a solution, by being dissolved in, for example,
methyl alcohol, ethyl alcohol, water, methylpropylglycol, or a mixed
solvent thereof. Acids or alkalis may be added to the solution, or the
solution may be concentrated. The compound may be added to an oil used in
a gelatin dispersion of a coupler. As disclosed in JP-A-59-174830,
preferably, the compound may be used in the form of a dispersion of fine
particles in a hydrophilic binder. In this case, the average diameter of
the fine particles is 0.001 to 5 .mu.m, preferably 0.01 to 2 .mu.m.
Preferably, these compounds are added to a silver halide emulsion layer.
They may be added to any layer, such as an intermediate layer, a
protective layer, a subbing layer, and an antihalation layer.
The amount of the compound to be added is generally 10.sup.-5 to 1 mole per
one mole of the silver halide, preferably in the range of
5.times.10.sup.-4 to 5.times.10.sup.-1 mole, and further preferably in the
range of 10.sup.-3 to 10.sup.-1 mole, when the compound is added to the
silver halide emulsion layer.
Further, when the compound is added to a layer other than the silver halide
emulsion layer, the compound is added preferably to give a concentration
10 times of the concentration of the above case.
These compounds may be added at any time of steps for preparing a
photographic emulsion, and at any stage after the preparation of an
emulsion to immediately before its coating. Preferably, they may be added
at the time of preparation of the coating solution; e.g., before, during,
or after the chemical sensitization, but after the addition of a
sensitizing dye.
Specific examples of the compound represented by general formulae (1) to
(5) are shown below, but the present invention is not limited to these
examples.
##STR3##
U.S. Pat. No. 3,649,267, JP-A-62-291642, JP-A-8-54705, JP-A-8-54724,
JP-A-9-218485, JP-A-10-90853, JP-A-10-90848, and the like, also disclose
specific examples of nitrogen-containing heterocyclic compounds.
The nitrogen-containing heterocyclic compounds that disclosed in U.S. Pat.
No. 3,649,267, JP-A-62-291642, JP-A-8-54705, and JP-A-8-54724 are metal
salts. Compared to the feature of the present invention, wherein the
existence of divalent metal ions in an amount equimolar or more to the
nitrogen-containing heterocyclic compound represented by general formulae
(1) to (5) is essential, when these antifoggants are used singly, much
desensitization occurs in usual color development processing, and effects
required in the present invention cannot be achieved. In these
publications/patents shown above, it is intended to prevent fogging of
light-sensitive materials in heat-development and/or diffusion transfer
processing. Therefore, they do not disclose the present invention which
attains suppression of fogging and high sensitivity at the same time, with
a (heat-developable) color light-sensitive material containing therein a
compound that forms a dye by a coupling reaction with the oxidization
product of a developing agent, and the developing agent built in the
material, in both heat-development and conventional color liquid
development.
The nitrogen-containing heterocyclic compound for use in the present
invention can be easily synthesized by a known method.
Examples of the halogen composition usable in the light-sensitive silver
halide emulsion for use in the present invention include silver chloride,
silver iodochloride, silver chlorobromide, silver iodochlorobromide,
silver iodobromide, and those having an arbitrary composition can be
preferably used. Further, other silver salts, for example, organic silver,
such as silver thiocyanate, silver sulfide, silver selenide, silver
carbonate, silver phosphate, benzotriazole silver, or the like, may be
included in the silver halide grains in the form of a solid solution, or
they may be junctioned.
The halogen composition may be uniform, or it may be different between the
inside and the surface of a grain. In the latter case, the silver halide
emulsion grain is a multiple-structure, laminated-structure grain, or the
like. Further, sliver halide emulsion grains having different compositions
may be joined by epitaxial junction.
A high-silver-chloride emulsion, having a silver chloride content of 50 mol
% or more, is generally characterized by high development activity. In
addition, such a silver chloride emulsion provides less haze on a image.
Therefore, the emulsion is preferable, because it is characterized to
exhibit less deterioration of the image information, when the developed
light-sensitive material is read by a scanner, without fixing. The silver
chloride content is preferably 70 mol % or more.
Those having localized phases that have different compositions, in a
layered or non-layered structure, inside and/or on the surface of silver
halide grains, may be used as well. The halogen composition of a localized
phase is analyzed by X-ray diffractometry, analytical electron microscopy,
and the like. The method of application of X-ray diffractometry to silver
halide is described, for example, in "Photographic Science and
Technology", by C. R. Berry and S. J. Marino, Vol. 2, p. 149, (1955), and
Vol. 4, p. 22, (1957). The localized phase can exist inside or at the
edges, corners, and planes of the surface of the grain, as one preferable
example, one formed by epitaxial junction in a corner of a grain can be
mentioned. Those examples are described in JP-A-58-108526, JP-A-59-133540,
JP-A-59-119350, JP-A-6-194768, and EP No. 0699944.
A light-sensitive material composed mainly of silver iodobromide is
desirable in terms of providing high sensitivity, as in the case of a
conventional light-sensitive material for photographing. In the case of
such a silver halide emulsion, it may also contain silver chloride. In
such a case, the silver chloride content is preferably 8 mol % or less,
and more preferably 3 mol % or less.
In the present invention, it is preferable to employ a light-sensitive
silver halide emulsion containing grains that have a laminated structure
comprising plural layers, which are different in halogen composition,
which grains contain inside a grain that has at least one layer having a
higher silver iodide content than either of the adjacent layer at the
inner side of the grain or the adjacent layer at the surface side of the
grain.
If a light-sensitive silver halide emulsion composed of silver
chlorobromide, silver chloride, or the like is used, silver iodide may be
contained therein, and, in this case the silver iodide content is
preferably 6 mol % or less, and more preferably 2 mol % or less.
Use of a light-sensitive emulsion having a high-silver-chloride content is
advantageous in terms of rapid processing, but, it is disadvantageous in
terms of adsorption of a sensitizing dye. However, the adsorption of the
sensitizing dye can be enhanced by making the composition of the surface
of the grain rich in silver iodide or silver bromide.
The halogen composition at the surface of a light-sensitive silver halide
emulsion grain is measured by X-ray photoelectron spectroscopy (ESCA).
The halogen composition distribution among the light-sensitive silver
halide emulsion grains (silver bromide content, silver iodide content, and
silver chloride content) is preferably narrow. The coefficient of
variation of the halogen composition distribution is preferably 3 to 30%,
more preferably 3 to 25%, and particularly preferably 3 to 20%. In this
connection, the above-mentioned coefficient of variation means a value
obtained by dividing a scattering (standard deviation) by an average.
The halogen composition distribution in each light-sensitive silver halide
emulsion can be analyzed by, for example, an X-ray microanalyzer (EPMA).
The shape of the silver halide grains can be chosen from regular crystals
having no twin plane, single twins having one twin plane, parallel
multiple twins having two or more parallel twin planes, non-parallel
multiple twins having two or more non-parallel twin planes, a spherical
shape, a potato-like shape, a tabular shape having a high-aspect ratio,
and a composite system thereof; and they are used in accordance with the
purpose. The shape of the twin grains is described in "Shashin Kogaku no
Kiso--Ginen Shashin-hen--", edited by Nihon Shashin-gakkai (Corona, Co.),
page 163. In the present invention, a tabular grain is preferable.
In the case of regular crystals, cubic grains having (100) planes,
octahedral grains having (111) planes, or dodecahedral grains having (110)
planes can be used. The dodecahedral grains are described in JP-B-55-42737
("JP-B" means examined Japanese patent application) and JP-A-60-222842.
These are also reported in "Journal of Imaging Science", Vol.30, page 247,
(1986). Grains having (h11) planes, (hh1) planes, (hk0) planes, or (hk1)
planes can be used, depending on the purpose. A 14-hedral grains having
(111) planes and (100) planes, and grains having (111) planes and (110)
planes, can be used as well. If necessary, polyhedron grains, such as
38-hedrons, eccentrically rhombic 24-hedrons, 46-hedrons, 68-hedrons, or
the like, can be used. In the high-silver-chloride content emulsion, to
produce a plane other than a (100) plane, a crystal-habit-controlling
agent is required. The formation of grains having a high-silver-chloride
content, and having {111} planes, (for example, with a method using
monopyridinium salts disclosed on pages 4 to 6 of JP-A-8-227117, or
bispyridinium salts disclosed in JP-A-2-32, as a crystal-habit-controlling
agent) is preferable in terms of the adsorption of dyes.
With respect to the shape of the tabular light-sensitive silver halide
grain in the light-sensitive silver halide emulsion, if principal (main)
planes (outer surfaces being parallel, and having the largest area) have
(111) planes, grains are those parallel multiple twins having 2 or more
parallel twin planes, and, if outer surfaces have (100) planes, they have
no twin plane. The interval between twin planes can be made 0.012 .mu.m or
less, as described in U.S. Pat. No. 5,219,720. Further, as described in
JP-A-5-249585, a value obtained by dividing a distance between (111)
principle planes by the interval between twin planes can be made 15 or
more.
If the above-mentioned principal planes are (111) planes, the shape of the
light-sensitive silver halide emulsion grain, when seen from above, is
circular shape, triangular shape, hexagonal shape, or roundishly circular
shapes formed from these shapes.
Even if the main planes are (111) planes, side planes connecting the main
planes may be (111) planes, (100) planes, or mixed-planes thereof, and
further, side planes may contain a plane having a larger index.
In a high-silver-chloride content emulsion, those having (111) planes as
main planes are preferable over those having (100) planes, in view of less
fogging.
If the outer surfaces are (100) planes, the shape of a light-sensitive
silver halide emulsion grain, when seen from above, is rectangular shape.
In the light-sensitive silver halide emulsion for use in the present
invention, preferably, the tabular light-sensitive silver halide grains
occupy 80 to 100% of the total projected area of the silver halide grains,
more preferably 90 to 100%, and particularly preferably 95 to 100%.
In the light-sensitive silver halide emulsion for use in the present
invention, the average grain thickness of the tabular light-sensitive
silver halide grains is preferably 0.005 to 0.2 .mu.m, and more preferably
0.01 to 0.15 .mu.m. In this connection, the above average grain thickness
means an arithmetic mean of the thickness of all tabular grains in the
light-sensitive silver halide emulsion.
In the light-sensitive silver halide emulsion, the circle-equivalent
diameter of the average projected area of the tabular light-sensitive
silver halide grains is preferably 0.2 to 8 .mu.m, more preferably 0.3 to
5 .mu.m, and particularly preferably 0.4 to 4 .mu.m.
The ratio of the circle-equivalent diameter to the average thickness of the
tabular light-sensitive silver halide grains in the light-sensitive silver
emulsion is called an "aspect ratio". The average aspect ratio of the
tabular light-sensitive silver halide grains according to the present
invention is preferably 3 to 100, and more preferably 6 to 80. The average
aspect ratio represents an arithmetic mean of the aspect ratios of all
tabular grains in the light-sensitive silver halide emulsion.
If the shapes of the projected area of the above-mentioned tabular
light-sensitive silver halide grains in the light-sensitive silver halide
emulsion are rectangular, the tabular grains, which have a ratio of a side
having a maximum length to side having a minimum length of 1 to 2, occupy
preferably 50 to 100% of the projected area of all grains, and more
preferably 70 to 100%. Further, tabular grains having an almost square
shape, in which the above ratio is nearly 1, are preferable.
The shape of the light-sensitive silver halide emulsion grains can be
measured by a transmission electron microscope, in accordance with a
carbon replica method, wherein both the light-sensitive silver halide
emulsion grains and a latex sphere for reference, which is used as a
standard for size, are simultaneously provided shadowing with heavy metals
or the like.
The use of a monodispersed light-sensitive silver halide emulsion having a
narrow distribution of grain size is preferable. The above-mentioned
monodispersed light-sensitive silver halide emulsion represents those
having coefficients of variation in the grain size distribution of 30% or
less. The method for using the monodispersed light-sensitive silver halide
emulsion is described in "Surfactant Science Series (Technological
applications of dispersions)", by Trevor Maternaghan, Vol. 52, p. 373,
(1994).
Further, a polydispersed light-sensitive silver halide emulsion having a
wide distribution of grain size may be used as well.
Moreover, as described in JP-A-1-167743 and JP-A-4-223463, for the purpose
of adjusting gradation, two or more types of monodispersed light-sensitive
silver halide emulsions, each having a different grain size but having
substantially the same color sensitivity, can be used in combination. Two
or more types of monodispersed light-sensitive silver halide emulsions can
be mixed in the same layer, or they may constitute layers separately. Two
or more types of polydispersed light-sensitive silver halide emulsions, or
a combination of a monodispersed light-sensitive silver halide emulsion
and a polydispersed light-sensitive silver halide emulsion, can be used.
Methods for preparing tabular grains having (111) planes, and comprising
silver bromide, silver iodobromide, or silver chlorobromide, are described
in JP-A-55-142329, JP-A-58-113926, JP-A-58-113927, JP-A-58-113928, U.S.
Pat. No. 4,914,014, U.S. Pat. No. 4,942,120, JP-A-2-222940, U.S. Pat. No.
5,013,641, and U.S. Pat. No. 4,414,306. Among these, methods for forming
tabular grains using a polyalkyloxide compound described in each
specification of U.S. Pat. Nos. 5,147,771 to 5,147,773, and U.S. Pat. Nos.
5,171,659, 5,210,013, and 5,252,453, are preferable.
To form tabular grains having a high average aspect ratio in the
light-sensitive silver halide emulsion, formation of a small-sized twin
nucleus is important. To form such a nucleus, the nucleus formation is
preferably carried out by making low temperature, high pBr, and low pH; by
reducing the amount of gelatin; by using a gelatin having a low methionine
content, a low-molecular gelatin, or a phthalated gelatin derivative; and
by shortening the time for the formation of the nucleus.
After the formation of nuclei, the nuclei of parallel multiple twins are
formed selectively through a physical ripening by allowing only the nuclei
of tabular grains (parallel multiple twin nuclei) to grow, and allowing
nuclei of other grains, i.e. nuclei of regular crystals, nuclei of single
twins, and nuclei of non-parallel multiple twins, to disappear. Then,
after adding a soluble silver salt and a soluble halide salt, or adding a
small-sized silver halide fine-grain emulsion, grains are grown, and the
light-sensitive silver halide emulsion containing the tabular grains is
prepared.
Preparation methods of tabular grains having (100) planes, and comprising
silver bromide or silver chlorobromide, are described in U.S. Pat. No.
4,063,951 (by T. G. Bogg), JP-A-58-95337 (by A. Mignot), JP-A-7-234470,
JP-A-8-339044, and JP-A-6-308648 (by Saito).
Tabular grains having (111) planes, and comprising a high-silver chloride
content emulsion, are described in U.S. Pat. Nos. 4,399,215, 4,400,463,
and 5,217,858, and JP-A-2-32. When a high-silver chloride is used,
ordinarily, outer surfaces become (100) planes, in a condition of no
adsorbable substance. Therefore, using an adsorbable substance having a
plane-selectivity on (111) planes, and, after allowing nuclei of twins to
form, then allowing nuclei of regular crystals, nuclei of single twins,
and nuclei of non-parallel multiple twins to disappear at a physical
ripening step, to obtain nuclei of parallel multiple twins selectively,
then grains are grown, and thereby a light-sensitive silver halide
emulsion containing the tabular grains is prepared.
Furthermore, a empirical rule of formation of silver chloride tabular
grains having (111) planes is reported in "Journal of Photographic
Science", Vol. 36, p. 182, (1988).
Tabular grains having (100) planes, and comprising high-silver content
emulsion grains are described in U.S. Pat. Nos. 4,946,772, 5,275,930, and
5,264,337, JP-A-5-281640, JP-A-5-313273, JP-A-6-308648, JP-A-7-234470,
JP-A-8-339044, and European Patent No.0534395A1. The formation of nuclei
that grow to be tabular is an important point, and it is effective to
conduct, at the initial stage of the grain formation, addition of bromide
ion or iodide ion, or addition of a compound exhibiting selective
adsorption on a specific plane. After the formation of the nuclei,
physical ripening and grain growth are conducted, to prepare a
light-sensitive silver halide emulsion containing the tabular grains. The
grain growth is carried out by adding soluble silver salt and soluble
halide salt, or a small-sized silver halide fine grain emulsion.
Since the surface area of such a tabular grain is larger than that of a
regular crystal having the same volume as the tabular grain, such a
tabular grain is able to increase the amount of sensitizing dyes to be
adsorbed, and thus it is advantageous in view of color sensitization
sensitivity. Accordingly, in contrast to regular crystal grain, the same
level of sensitivity can be obtained with smaller volume. Further, as the
number of grains increases, the number of a starting site of development
increases, thus excellent graininess, which is an important property in a
light-sensitive material for photography, can be obtained. Further, by
virtue of the excellent graininess as described above, reduction of the
coating amount of silver is possible, and thus the tabular grain is
excellent in prevention of radiation fogging, which has been a problem of
a light-sensitive material for high-sensitivity photography.
Reducing the coating amount of silver is effective to reduce haze that
causes the deterioration of image information, when the image is read by a
scanner from a processed light-sensitive material that is not fixed.
Since the tabular grains have a large specific surface area, they are
characterized by having high developing activity. Moreover, the tabular
grains align in orientation at the time of application, making it possible
to make a light-sensitive material to be a thin-layer, and the obtained
photographic material is excellent in sharpness. Thus, the tabular grain
is an indispensable emulsion grain for a light-sensitive material for
photographing.
As long as resistance to damage by pressure and monodispersibility of grain
distribution are not damaged, tabular grains having a larger average
aspect ratio are preferable, in terms of sensitivity, graininess,
activity, and reduction of the amount of silver to be coated.
The tabular light-sensitive silver halide grains, in the light-sensitive
silver halide emulsion for use in the present invention, may have
dislocation lines.
A technology to introduce dislocation lines with control is described in
JP-A-63-220238. The tabular grains wherein dislocation lines have been
introduced are excellent in photographic characteristics, such as
sensitivity, reciprocity law, etc., in contrast to tabular grains having
no dislocation lines. Preferable methods to introduce dislocation lines
are described in U.S. Pat. Nos. 5,498,516, 5,496,694, and 5,527,664. It is
preferable to use the tabular grains prepared by using these technologies
for the present invention.
If the tabular grains in the light-sensitive silver halide emulsion used in
the present invention have dislocation lines, the place can be arbitrarily
selected from limited introduction at a top portion, or a fringe portion
of the grain, or introduction to whole portions of the main plane of the
grain, or the like. Particularly preferably, the place is to be limited to
the fringe portion.
In the present invention, the fringe portion of grain represents an outer
periphery of a tabular grain. In detail, in the distribution of silver
iodide extending from an edge to the center of the tabular grain, the
fringe portion represents an outer region of a point where the silver
iodide content first becomes higher or lower than the average content of
silver iodide of the whole grain, when seen from the edge of the tabular
grain.
In the present invention, if the tabular grain has dislocation lines, the
density of the dislocation lines may be arbitrarily selected, i.e., any
number of dislocation lines per one grain can be selected, depending on
each case, from, for example, 10 or more, 30 or more, 50 or more, etc.
As a protective colloid that is used when the emulsion according to the
present invention is prepared, gelatin is used advantageously, but another
hydrophilic binder can also be used. The hydrophilic binder can be used
singly or in combination with gelatin. As a hydrophilic binder,
preferable, use can also be made of, for example, a gelatin derivative, a
graft polymer of gelatin with another polymer, a protein, such as albumin
and casein; a cellulose derivative, such as hydroxyethylcellulose, and
cellulose sulfate ester; sodium alginate, a starch derivative, a
polysaccharide, carrageenan, and synthetic hydrophilic polymers, including
homopolymers and copolymers, such as a polyvinyl alcohol, a modified
alkylpolyvinyl alcohol, a polyvinyl-N-pyrrolidone, a polyacrylic acid, a
polymethacrylic acid, a polyacrylamide, a polyvinylimidazole, a
polyvinylpyrazole, and thioether polymer described in U.S. Pat. No.
3,615,624.
As a gelatin, in addition to lime-processed gelatin, acid-processed
gelatin, de-ashed gelatin, gelatin derivatives, such as, phthalated
gelatin, trimellitated gelatin, carbamoyl gelatin, succinated gelatin,
esterified gelatin, and gelatin that is low-molecular, can be used when
the tabular grains are formed. It is known that gelatin subjected to
oxidation treatment with an oxidizing agent, such as hydrogen peroxide, is
useful in forming tabular grains. In addition, a gelatin treated with an
enzyme, as described in "Bull. Soc. Photo. Japan" No. 16, p. 30, (1966),
can be used as a low-molecular gelatin. Hydrolyzate or enzymolyzate of
gelatin can also be used.
In the process of grain formation or physical ripening of silver halide,
metal salt (including complex salt) can be coexisted. Examples of the
metal salt include, salt or complex salt of noble metal or metal, such as
cadmium, zinc, lead, thallium, iridium, platinum, palladium, osmium,
rhodium, chromium, ruthenium, rhenium, cobalt, gallium, copper, nickel,
manganese, indium, tin, calcium, strontium, barium, aluminum, bismuth or
the like. These compounds may be used singly or in a combination of 2 or
more kinds. The amount to be added is around 10.sup.-9 to 10.sup.-3 moles
per mole of the silver halide. These metals may be used in the form of a
water-soluble salt, such as a six-coordinate complex, or a four-coordinate
complex salt or an ammonium salt, an acetate, a nitrate, a sulfate, a
phosphate, or a hydrochloride. Examples of complex ion and coordinate
compounds that can be preferably used include bromide ion, chloride ion,
cyanide ion, nitrosyl ion, thiocyanide ion, thionitrosyl ion, water,
ammonia, oxo, carbonyl, or the like, and combinations thereof. For
example, yellow prussiate of potash, K.sub.2 IrCl.sub.6, K.sub.3
IrCl.sub.6, (NH.sub.4).sub.2 RhCl.sub.5 (H.sub.2 O), K.sub.2 RuCl.sub.5
(NO), K.sub.3 Cr(CN).sub.6, K.sub.4 Ru(CN).sub.6, CdCl.sub.2, Pb(CH.sub.3
COO).sub.2, or the like can be preferably used. Further, the position of a
silver halide grain to which these compounds are incorporated, may be
uniformly inside of the grain, or may be a localized position at the
surface or inside, etc., of the grain, or a localized phase of silver
bromide, or a high-silver-chloride grain-base. The addition method of
these compounds includes a method wherein an aqueous solution of halide,
or a solution of a water-soluble silver salt, for use at the time of grain
formation, is mixed with a solution of the above metal salt, and then the
mixture is added continuously during the grain formation; a method wherein
silver halide emulsion fine grains to which the above metal ions are
doped, are added; or a method wherein the solution of the above metal salt
is directly added, before, during, or after the formation of the grains.
During the formation of the grains, the above metal salt solution can be
continuously added.
In some cases, a method wherein a chalcogenide compound is added during the
preparation of the emulsion, as described in U.S. Pat. No. 3,772,031, is
also useful. In addition to S, Se, and Te, a cyanate, a thiocyanate, a
selenocyanate, a carbonate, a phosphate, or an acetate may be present.
The light-sensitive silver halide emulsion in the present invention can be
used even if it is not chemically sensitized; however, generally it is
used after being chemically sensitized. The chemical sensitization methods
used in the present invention include the chalcogen sensitization method,
such as the sulfur sensitization method, the selenium sensitization
method, and the tellurium sensitization method; the noble metal
sensitization method using gold, platinum, palladium, or the like; and the
reduction sensitization method, and they can be used singly or in
combination (e.g. JP-A-3-110555 and JP-A-5-241267). These chemical
sensitizations can be carried out in the presence of a nitrogen-containing
heterocyclic compound (JP-A-62-253159). Further, the below-mentioned
antifoggant can be added after the completion of the chemical
sensitization. Specifically, methods described in JP-A-5-45833 and
JP-A-62-40446 can be used.
In the present invention, there is no limitation on pAg and pH of an
emulsion on which sulfur sensitization, selenium sensitization or
tellurium sensitization, and gold sensitization are conducted. However,
preferably, the pAg is in the range of 5 to 11, while the pH is in the
range of 3 to 10; more preferably the pAg is in the range of 6.8 to 9.0,
while the pH is in the range of 5.5 to 8.5.
When gold sensitization is performed by using a metal ion of a cyano
complex, at the time of the grain formation, to achieve high sensitivity,
the addition of a metal ion, such as a zinc ion, that coordinates to
gelatin, at the time before chemical sensitization or at the time of the
dispersion of gelatin, is preferable.
For the purpose of preventing fogging and of increasing stability during
storage, an antifoggant and a stabilizer may be added to the silver halide
emulsion. The details of these compounds are described in "The Theory of
the Photographic Process", by T. H. James, P.396-P.399, Macmillan (1977),
and its references.
The timing when the antifoggant or the stabilizer is added to the silver
halide emulsion may be at any stage in the preparation of the emulsion.
The addition to the emulsion can be carried out at any time, singly or in
combination, of after the completion of the chemical sensitization and
during the preparation of a coating solution, at the time of the
completion of the chemical sensitization, during the chemical
sensitization, prior to the chemical sensitization, after the completion
of the grain formation and before desalting, during the grain formation,
or prior to the grain formation.
These antifoggant and stabilizer can be used also for the purpose of
control of crystal habit, prevention of dissolution, and preparation of
small sized emulsion grains; control of chemical sensitization; control of
the alignment of sensitizing dye, in addition to the effects they
originally have, such as prevention of fogging, or stabilization.
The amount of these antifogging agents or stabilizers to be added varies in
accordance with the halogen composition of the silver halide emulsion and
the purpose, and it is generally in the range of 10.sup.-6 to 10.sup.-1
mol, and preferably 10.sup.-5 to 10.sup.-2 mol, per mol of the silver
halide.
In the present invention, preferably so-called spectral sensitization, for
sensitizing the light-sensitive silver halide emulsion to a desired light
wavelength range, is carried out. Particularly, in a color photographic
light sensitive material, for color reproduction faithful to the original,
light-sensitive layers having light sensitivities to blue, green, and red
are incorporated. These sensitivities are provided by spectrally
sensitizing the silver halide. In the spectral sensitization, use is made
of a so-called spectrally sensitizing dye that is adsorbed to the silver
halide grains, to cause them to have sensitivity in the range of its own
absorption wavelength.
Dyes that can be used include a cyanine dye, a merocyanine dye, a composite
cyanin dye, a composite merocyanine dye, a holopolar cyanine dye, a
hemicyanine dye, a styryl dye, and a hemioxonol dye. Particularly useful
dyes are those belonging to a cyanine dye, a merocyanine dye, and a
composite merocyanine dye. In these dyes, any of nuclei generally used in
cyanine dyes as base heterocyclic nuclei can be applied. That is, a
pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole
nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an
imidazole nucleus, a tetrazole nucleus, and a pyridine nucleus; and a
nucleus formed by fusing an cycloaliphatic hydrocarbon ring to these
nuclei; a benzindolenine nucleus, an indole nucleus, a benzoxazole
nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a
naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole
nucleus, a quinoline nucleus, can be applied. These nuclei may be
substituted on the carbon atom.
In the merocyanine dye or the composite merocyanine dye, as a nucleus
having a ketomethylene structure, for example, a 5- to 6-membered
heterocyclic nucleus, such as a pyrazolin-5-one nucleus, a thiohydantoine
nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione
nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus, can be
applied.
Typical examples of sensitizing dye are described in U.S. Pat. No.
4,617,257, JP-A-59-180550, JP-A-64-13546, JP-A-5-45828, JP-A-5-45834, or
the like.
The sensitive dyes for use in the present invention is known in the art and
can be synthesized with reference to the following literature.
(a) F. M. Hamer; "Heterocyclic Compounds--Cyanine Dyes and related
compounds" (John Wiley & Sons--New York, London, 1964)
(b) D. M. Sturmer; "Heterocyclic Compounds--Special Topics in heterocyclic
chemistry" (John Wiley & Sons--New York, London, 1977)
These spectral sensitizing dyes can be used singly or in combination, and a
single use or a combination use of these sensitizing dyes is selected for
the purpose of adjusting the wavelength distribution of the spectral
sensitivity, and for the purpose of supersensitization. When using a
combination of the dyes having supersensitizing effect, it is possible to
attain sensitivity much larger than the sum of sensitivities that can be
attained by each single dye. Further, together with the sensitizing dye,
it is also preferable to use a dye having no spectral sensitizing action
itself, or a compound that does not substantially absorb visible light and
that exhibits supersensitization. As an example of the supersensitizer, a
diaminostilbene compound and the like can be mentioned. These examples are
described, for example, in U.S. Pat. No. 3,615,641 and JP-A-63-23145.
The timing when the spectral sensitizing dye or the supersensitizer is
added to the emulsion may be at any stage in the preparation of emulsions.
The addition is carried out most usually at a time after the completion of
chemical sensitization and before coating, but it can be carried out at
the same time as the addition of a chemical sensitizer, to carry out
spectral sensitization and chemical sensitization simultaneously, as
described in U.S. Pat. Nos. 3,628,969 and 4,225,666; or it can be carried
out prior to chemical sensitization, as described in JP-A-58-113,928.
Further, it can be carried out before the completion of the formation of
the precipitate of silver halide grains, to start spectral sensitization.
Furthermore, as taught in U.S. Pat. No. 4,225,666, these foregoing
compounds may be added in portions, i.e., partial addition that stretches
over the steps, for example, part of these compounds is added prior to
chemical sensitization, and the rest is added after the chemical
sensitization; and also the addition may be carried out at any time during
the formation of silver halide grains, as disclosed, for example, in U.S.
Pat. No. 4,183,756.
The addition at a step before the chemical sensitization is preferable to
obtain high sensitivity.
The amount of the spectral sensitizing dye or the supersensitizer to be
added may vary depending on the shape of the grains, the size of the
grains, and the desired photographic properties, and it is generally in
the range of 10.sup.-8 to 10.sup.-1 mol, and preferably 10.sup.-5 to
10.sup.-2 mol, per mol of the silver halide.
These sensitizing dyes or supersenstizer can be added in the form of a
solution of a hydrophilic organic solvent, such as methanol, alcohol
containing fluorine, or methylproylglycol; as an aqueous solution, or as a
mixture thereof. To increase solubility or preservability, these solutions
may be adjusted to make them alkaline or acidic. They may be added in the
form of an aqueous solution, using a surface-active agent, as described in
JP-B-49-44. They may also be added in the form of a powder, prepared by
dissolving the sensitizing dye, to mix with a dispersant, removing an
auxiliary solvent or the like, and then drying the resultant, to be a
powder, as described in JP-A-49-128725 and JP-B-49-8330. They may be added
by allowing the dye to adsorb on fine particles of silica, as described in
U.S. Pat. No. 3,649,286. They may be added by a method wherein, after
adding an auxiliary dispersing agent, such as sorbitol, or a
surface-active agent, to the dye, in water, the mixture is mechanically
ground and dispersed, to be a slurry, and the mixture is dryed, and then
it is added, as described in U.S. Pat. No. 4,006,025, JP-A-52-110012,
JP-A-53-102733, and JP-A-53-102732. Moreover, they can be added by a
method wherein, after mechanically grinding the sensitizing dye to make it
1 .mu.m or less, and dispersing it, then the dispersion is further
dispersed in a hydrophilic colloid, such as gelatin, which acts as an
auxiliary dispersing agent, as described in JP-A-58-105141.
In order to reinforce the adsorption of the sensitizing dye, a soluble
calcium compound, a soluble bromine compound, a soluble iodine compound, a
soluble chlorine compound, or a soluble thiocyanate compound may be added
before, after, and during the addition of the sensitizing dye. These
compounds may be used in combination. Preferable examples of these
compounds include CaCl.sub.2, KI, KCl, KBr, and KSCN. These compounds may
be in the state of fine particles of silver bromide, silver chlorobromide,
silver iodobromide, silver iodide, and silver rhodanide emulsion
particles.
Such additives for photography that can be used in the light-sensitive
material of the present invention are described in more detail in Research
Disclosures (hereinafter abbreviated to as RD) No. 17643 (December 1978),
RD No. 18716 (November 1979), and RD No. 307105 (November 1989), and the
particular parts are shown below.
______________________________________
Kind of Additive
RD 17643 RD 18716 RD 307105
______________________________________
Chemical p. 23 p. 648 (right
p. 866
sensitizers column)
Sensitivity- -- p. 648 (right --
enhancing agents column)
Spectral pp. 23-24 pp. 648 (right pp. 866-868
sensitizers and column)-649
Supersensitizers (right column)
Brightening p. 24 pp. 648 (right p. 868
agents column)
Antifogging pp. 24-26 p. 649 (right pp. 868-870
agents and column)
Stabilizers
Light absorbers, pp. 25-26 pp. 649 (right p. 873
Filter dyes, and column)-650
UV Absorbers (left column)
Image dye p. 25 p. 650 (left p. 872
stabilizers column)
Hardeners p. 26 p. 651 (left pp. 874-875
column)
Binders p. 26 p. 651 (left pp. 873-874
column)
Plasticizers and p. 27 p. 650 (right p. 876
Lubricants column)
Coating aids and pp. 26-27 p. 650 (right pp. 875-876
Surfactants column)
Antistatic agents p. 27 p. 650 (right pp. 876-877
column)
Matting agents -- -- pp. 878-879
______________________________________
Usually the total amount of the light-sensitive silver halide used in the
light-sensitive material is 0.05 to 20 g/m.sup.2, and preferably 0.1 to 10
g/m.sup.2, in terms of silver.
In the present invention, the light-sensitive silver halide may be used
together with an organic metal salt as an oxidizing agent. Among such
organic metal salts, organosilver salt is particularly preferably used.
As the organic compound that can be used to form the above organosilver
salt oxidizing agent, benzotriazoles, aliphatic acids, and other
compounds, as described in U.S. Pat. No. 4,500,626, columns 52 to 53, can
be mentioned. Also useful is acetylene silver described in U.S. Pat. No.
4,775,613. Organosiliver salts may be used in the form of a combination of
two or more.
The above organosilver salts may be used additionally in an amount of
generally 0.01 to 10 mol, and preferably 0.01 to 1 mol, per mol of the
light-sensitive silver halide.
As the binder of the constitutional layer of the light-sensitive material,
a hydrophilic binder is preferably used. Examples thereof include those
described in the above-mentioned Research Disclosures and JP-A-64-13546,
pages (71) to (75). Specifically, a transparent or semitransparent
hydrophilic binder is preferable, and examples include natural compounds
such as proteins including gelatin, gelatin derivatives and the like, or
polysaccharides including cellulose derivatives, starches, gum-arabic,
dextrans, pullulan, and the like; and synthetic polymer compounds such as
polyvinyl alcohols, modified polyvinyl alcohols (e.g.
terminal-alkyl-modified POVAL MP103, MP203 and the like, trade name,
manufactured by Kuraray Co., Ltd.), polyvinyl pyrrolidones, and acrylamide
polymers. Further, highly water-absorptive polymers described, for
example, in U.S. Pat. No. 4,960,681, and JP-A-62-245260; that is,
homopolymers of vinyl monomers having --COOM or --SO.sub.3 M (M represents
a hydrogen atom or an alkali metal), or copolymers of these vinyl
monomers, or copolymers of the vinyl monomer(s) with another vinyl monomer
(e.g., those comprising sodium methacrylate or ammonium methacrylate,
including Sumika Gel L-5H, trade name, manufactured by Sumitomo Chemical
Co., Ltd.) can also be used. Two or more of these binders can be used in
combination. Particularly, combinations of gelatin with the above binders
are preferable. Further, the gelatin can be selected from lime-processed
gelatin, acid-processed gelatin; so-called de-ashed gelatin from which the
calcium content, etc., have been reduced; low-molecular gelatin having a
small molecular weight, and gelatin derivatives, such as phthalated
gelatin, acylated gelatin, and esterified gelatin, in accordance with
various purposes, and combinations thereof are also preferable.
In the present invention, the amount of a binder to be applied is 1 to 20
g/m.sup.2, preferably 2 to 15 g/m.sup.2, and further preferably 3 to 12
g/m.sup.2.
According to the present invention, image-forming substances may be
developed silver, and also dyes (dye-providing compounds) can be used as
the image-forming substances. Using dye-providing compounds that form or
release dyes, a monochromatic picture image formed by dyes can also be
obtained.
As the reducing agent that can be used in the present invention, known
reducing agents in the field of a heat-developable light-sensitive
material can be used. Further, the later-described dye-providing compounds
having reducibility are also included (in this case, other reducing agent
can be used additionally). Further, reducing agent precursors that have no
reducibility themselves but exhibit reducibility by the action of heat or
a nucleophilic agent during the process of development can be used.
Examples of the reducing agent used in the present invention include
reducing agents and reducing agent precursors described, for example, in
U.S. Pat. No. 4,500,626, columns 49 to 50, U.S. Pat. No. 4,839,272, U.S.
Pat. No. 4,330,617, U.S. Pat. No. 4,590,152, U.S. Pat. No. 5,017,454, U.S.
Pat. No. 5,139,919, JP-A-60-140335, pages (17) to (18), JP-A-57-40245,
JP-A-56-138736, JP-A-59-178458, JP-A-59-53831, JP-A-59-182449,
JP-A-59-182450, JP-A-60-119555, JP-A-60-128436, JP-A-60-128439,
JP-A-60-198540, JP-A-60-181742, JP-A-61-259253, JP-A-62-201434,
JP-A-62-244044, JP-A-62-131253, JP-A-62-131256, JP-A-63-10151,
JP-A-64-13546, pages (40) to (57), JP-A-1-120553, JP-A-2-32338,
JP-A-2-35451, JP-A-2-234158, JP-A-3-160443, and EP-A-220 746, pages 78 to
96.
Combinations of various reducing agents as disclosed in U.S. Pat. No.
3,039,869 can also be used.
Examples of a developing agent that form color by coupling reaction with a
coupler are p-phenylenediamines, p-aminophenols, and so on. More
preferable examples are sulfonamidophenols described in JP-A-8-110608,
JP-A-8-122994, JP-A-8-146578, JP-A-9-15806, and JP-A-9-146248;
sulfonylhydrazines described in EP-A-545,491A, JP-A-8-166664, and
JP-A-8-227131; carbamoylhydrazines described in JP-A-8-286340;
sulfonylhydrazones described in JP-A-8-202002, and carbamoylhydrazones
described in JP-A-8-234390.
The color-developing agent may be used singly or in a combination of two or
more kinds of the agents, and its total amount to be used is generally
0.05 to 20 millimoles/m.sup.2, and preferably 0.1 to 10
millimoles/m.sup.2.
In the light-sensitive material, couplers that form dyes by coupling
reaction with the above-mentioned oxidized product of the above
color-developing agent, are generally used. Preferable examples include
compounds that are collectively referred to as active methylenes,
5-pyrazolones, pyrazoloazoles, phenols, naphthols, and pyrrolotriazoles.
The specific examples described in RD No. 38957 (September 1996), on pages
616 to 624, may be used preferably. As particularly preferable examples,
pyrazoloazole couplers, as described in JP-A-8-110608, and pyrrolotriazole
couplers, as described in JP-A-8-122994 and JP-A-8-45564, can be
mentioned. These couplers are generally used in an amount of 0.05 to 10
millimole/m.sup.2 and preferably 0.1 to 5 millimole/m.sup.2, for each
color.
Furthermore, a colored coupler to rectify unnecessary absorption of
color-forming dyes, and a compound (including coupler) that releases a
photographically useful compound residue, for example, a development
inhibitor, by a reaction with the oxidized product of the developing
agent, can be used as well.
Further, as one mode of the present invention, the light-sensitive material
can be configured such that it comprises, on a support, a
non-light-sensitive layer and at least one layer of a light-sensitive
silver halide emulsion layer, which comprises a light-sensitive silver
halide emulsion, a coloring material that releases or diffuses a
diffusible dye correspondingly or inversely-correspondingly to silver
development, and a binder.
The coloring material used in this occasion is a compound containing a dye
component in its structure itself, and having a capability to release or
diffuse a diffusible dye correspondingly or inversely-correspondingly to
silver development.
Part or all of the diffusible dyes is removed from the light-sensitive
material, simultaneously or successively with the development. An image is
obtained by a residual coloring material after development, in the
light-sensitive material.
This compound can be represented by the following general formula [LI]:
((Dye)m-Y)n-Z [LI]
Dye represents a dye group, a dye group whose wavelength is temporarily
shortened, or a dye precursor group, Y represents a single bond or a
linking group, Z represents a group which has such a property that
produces a difference in the diffusibility of the compound represented by
((Dye)m-Y)n-Z correspondingly or inversely-correspondingly to the
light-sensitive silver salt having a latent image imagewise, or that
releases (Dye)m-Y, to produce a difference in the diffusibility between
(Dye)m-Y released and ((Dye)m-Y)n-Z, m is an integral number of 1 to 5, n
is 1 or 2, and when both m and n is not 1, a plurality of Dyes are the
same or different.
As specific examples of the dye-providing compound represented by the
general formula [LI], compounds 1 to 5 described in JP-A-9-121265 (p.
10-p. 21) can be mentioned. In this connection, the compounds 1 to 3 are
those that release or diffuse the diffusible dyes
inversely-correspondingly to the development of silver halide, while the
compounds 4 to 5 are those that release or diffuse the diffusible dye
correspondingly to the development of silver halide. Further, as described
in U.S. Pat. Nos. 4,362,806, 3,719,489, and 4,375,507, a compound that
reacts with silver ion or organosilver ion complex to release a diffusible
dye, can be used.
A light-sensitive material is usually comprising three or more types of
phosensitive layers, each being different in color sensitivity. Each
photosensitive layer contains at least one silver halide emulsion layer,
and as a typical example, it comprises plural silver halide emulsion
layers, whose color sensitivities are substantially identical but whose
sensitivities are different. The photosensitive layer is a unit
photosensitive layer having color sensitivity to any of blue light, green
light, or red light. In a multilayer silver halide color photographic
light-sensitive material, in general, the arrangement of the unit
photosensitive layer is such that a red-sensitive layer, a green-sensitive
layer, and a blue-sensitive layer in the order started from the support
side are placed. However, depending on purposes, the above order can be
reversed, and an order wherein a layer having a different color
sensitivity is placed between light-sensitive layers having the same color
sensitivity, can be used.
In the present invention, a yellow filter layer, a magenta filter layer,
and an antihalation layer can be used as a colored layer using oil-soluble
dyes, which can be decolored by development processing. If, for example,
the light-sensitive layers are provided in the order of a red-sensitive
layer, a green-sensitive layer, and a blue-sensitive layer, from the side
nearest to the support, a yellow filter layer can be provided between the
blue-sensitive layer and the green-sensitive layer, a magenta color filter
layer can be provided between the green-sensitive layer and the
red-sensitive layer, and a cyan color filter layer (antihalation layer)
can be provided between the red-sensitive layer and the support. These
colored layers may be arranged in a manner that they directly contact a
light-sensitive layer (an emulsion layer), or in a manner they contact to
a light-sensitive layer through an intermediate layer, such as gelatin.
The amount of a dye to be used is a sufficient amount to make the
transmission density of each layer be 0.03 to 3.0, more preferably 0.1 to
1.0, to blue light, green light, or red light, respectively. More
concretely, the amount is, though it varies depending on the .epsilon.
value and the molecular weight of the dye, generally in the range of 0.005
mmol/m.sup.2 to 2.0 mmol/m.sup.2, and more preferably 0.05 mmol/m.sup.2 to
1.0 mmol/m.sup.2.
Preferable examples of the dye to be used, as disclosed in JP-A-10-207027,
include (NC).sub.2 C.dbd.C(CN)--R.sub.16 (R.sub.16 represents an aryl
group or heterocyclic group), and a compound having a structure which
comprises methine groups and two kinds of groups selected from: aryl
groups (e.g. phenyl group and naphthyl group), and heterocyclic groups
(e.g. pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine,
quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole,
pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxadiazole,
benzoquinoline, thiaziazole, pyrrolothiazole, pyrrolopyridazine,
tetrazole, oxazole, coumarin, chroman); basic nulei (e.g. pyridine,
quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole,
benzoimidazole, benzothiazole, oxazoline, naphthooxazole or pyrrole); and
acidic nuclei including compounds having a methylene group placed between
electron-attracting groups (e.g. a methylene group placed between groups
such as --CN, --SO.sub.2 R.sub.14, --COR.sub.14, --COOR.sub.14,
--CON(R.sub.15).sub.2, --SO.sub.2 N(R.sub.15).sub.2, --C[.dbd.C(CN).sub.2
]R.sub.14, and --C[.dbd.C(CN).sub.2 ]N(R.sub.14).sub.2 (R.sub.14 each
represents an alkyl group, an alkenyl group, an aryl group, a cycloalkyl
group, and heterocyclic group, and R.sub.15 represents a hydrogen atom or
groups shown for R.sub.14)) and cyclic ketomethylene compounds (e.g.,
2-pyrazoline-5-one, 1,2,3,6-tetrahydropyridine-2,6-dione, rhodanine,
hydantoin, thiohydantoin, 2,4-oxazolidinedione, isooxazolone, barbituric
acid, thiobarbituric acid, indandione, dioxopyrazolopyridine,
hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2-one and
pyrroline-2-one).
Two or more kinds of dye may be used as a mixture in one colored layer of
the light-sensitive member. For example, a mixture of three kinds of dye,
including yellow, magenta, and cyan dye, can be added to the antihalation
layer described above.
According to the present invention, preferably, a color-extinguishable-dye
is used in the form of a dispersion, in which oil drops that include a
color-extinguishable-dye dissolved in an oil and/or oil-soluble polymer,
are dispersed in a hydrophilic binder. As a preparation method of the
above, an emulsification and dispersion method is preferable, and the
preparation can be conducted, for example, according to the method
disclosed in U.S. Pat. No. 2,322,027. In this case, a high-boiling oil, as
disclosed in U.S. Pat. Nos. 4,555,470, 4,536,466, 4,587,206, 4,555,476,
and 4,599,296, JP-B-3-62,256, etc., can be used, if necessary, in
combination with a low-boiling organic solvent having a boiling point of
50 to 160.degree. C. Simultaneous use of two or more kinds of high-boiling
oils is possible. An oil-soluble polymer can be used instead of the oil or
in combination with the oil. An example is described in PCT WO88/00723.
The amount of the high-boiling oil and/or the polymer to be used is
generally 0.01 to 10 g, preferably 0.1 to 5 g, per 1 g of the dye to be
used.
The color of the dye disappears when developed in the presence of a
color-extinguishing agent.
Examples of the color-extinguishing agents include alcohols or phenols,
amines or anilins, sulfinic acids or salt thereof, sulfurous acids or salt
thereof, thiosulfuric acids or salt thereof, carboxylic acids or salt
thereof, hydrazines, guanidines, aminoguanidines, amidines, thiols,
cyclic- or chain-like active methylene compounds, cyclic- or chain-like
active methine compounds, and anions derived from these compounds.
Among the above, hydroxyamines, sulfinic acids, sulfurous acids,
guanidines, aminoguanidines, heterocyclic thiols, cyclic- or chain-like
active methylene compouns, or cylic- or chain-like active methine
compounds are preferably used, and particularly preferably guanidines or
aminoguanidines are used.
The above color-extinguishing agent extinguish a dye color by contacting
the dye at development treatment, and then by being added nucleophilically
to the dye molecule. Preferably, by overlaying the surface of film of a
silver halide light-sensitive member containing the dye, at the time after
image-wise exposure, or at the same time as image-wise exposure, with the
surface of a processing member (first processing member described later)
containing the color-extinguishing agent or color-extinguishing agent
precurser, in the presence of water, heating those members, and then
separating them, a colored image is obtained on the silver halide
light-sensitive member, and the dye is extinguished, simultaneously. In
this case, the density of the dye after extinction is generally one-third
or below the original density, preferably one-fifth or below. The amount
of the color-extinguishing agent is generally 0.1 to 200 times, more
preferably 0.5 to 100 times, per mole of the dye.
The sum of the thickness of the light-sensitive layers is generally 1 to 20
.mu.m, and preferably 3 to 15 .mu.m.
The silver halide, the color-developing agent, and the coupler may be
contained in the same or different light-sensitive layers. Moreover, in
addition to the light-sensitive layer, non-light sensitive layers, such as
a protective layer, a subbing layer, an intermediate layer, and the
above-mentioned yellow filter layer and an antihalation layer, can be
provided; and a backing layer may be provided on the rear side of the
support. The thickness of all of the applied films on the side of the
light-sensitive layer is generally 3 .mu.m to 25 .mu.m, preferably 5 .mu.m
to 20 .mu.m.
Depending on various purposes, a hardening agent, a surfactant, a
photographic stabilizer, an antistatic agent, a slipping agent, a matting
agent, a latex, a formalin scavenger, a dye, and a UV absorbing agent may
be used in the light-sensitive material. Specific examples of these are
described in the above-mentioned RD, and in JP-A-9-204031, etc. Further,
particularly preferable examples of the antistatic agent include fine
particles of metal oxides, such as ZnO, TiO.sub.2, Al.sub.2 O.sub.3,
In.sub.2 O.sub.3, SiO.sub.2, MgO, BaO, MOO.sub.3, V.sub.2 O.sub.5, and the
like.
As a support for a light-sensitive material, supports for photography
described in "Shasin Kogaku no Kiso--Ginen Shashin-hen", edited by Nihon
Shashin-gakkai, pages 223-240, Corona, Co. (1979), are preferable.
Specific examples include polyethylene terephthalate, polyethylene
naphthalate, polycarbonate, syndiotactic polystyrene, celluloses (e.g.
triacetylcellulose), and the like.
To improve optical characteristics and physical characteristics of these
supports, heat treatment (for control of the degree of crystalinity and
orientation), uniaxial and biaxial stretching (for control of
orientation), blending of various types of polymers, surface treatment, or
the like, may be performed.
Further, it is preferable to record photographing information by using a
support that has a magnetic recording layer, as described in
JP-A-4-124645, JP-A-5-40321, JP-A-6-35092, and JP-A-6-31875.
Preferably, a water-resistant polymer, as described in JP-A-8-292514, is
applied on the rear side of the support of the light-sensitive material.
Details of a polyester support that is used particularly preferably in a
light-sensitive material having the above magnetic recording layer, are
described in Kokai Giho No. 94-6023 (Hatsumei-Kyokai; 1994.3.15).
The thickness of the support is generally 5 to 200 .mu.m, and preferably 40
to 120 .mu.m.
In the present invention, when the light-sensitive material through which
shooting has been made is developed, a processing material other than the
light-sensitive material can be used. The processing material contains at
least a base and/or a base precursor. The most preferable ones thereof are
systems described in EP-210 660 and U.S. Pat. No. 4,740,445 wherein a base
is generated by means of a combination of a basic metal compound
difficultly soluble in water with a compound that can undergo a complex
formation reaction with the metal ion constituting the basic metal
compound using water as a medium. In this case, although preferably the
basic compound difficultly soluble in water is added to the
light-sensitive material and the complex forming compound is added to the
processing material, that can be reversed. A preferable combination of
compounds is a system wherein fine particles of zinc hydroxide are used in
the light-sensitive material and a salt of picolinic acid, such as
guanidine picolinate, is used in the processing material.
A mordant may be used in the processing material, and in this case, a
polymer mordant is preferable. As described in JP-A-8-179458, use can be
made of a method wherein physical-development-nucleus such as colloidal
silver and palladium sulfide, and a silver halide solvent such as
hydantoin, may be contained in the processing material, and by
solubilizing the silver halide in the light-sensitive material at the time
of development to fix it on the processing material.
Additionally, the processing material may contain a development-stopping
agent, a printout-preventing agent, or the like.
The processing material may comprise, in addition to the processing layer,
auxiliary layers such as a protective layer, a subbing layer, a backing
layer, and other layers.
As a form of the processing material to practise, a form wherein the
processing layer is provided on a continuous web, and the processing
material is fed from a feeding roll and is wound up by a separate roll
without being cut even after having been used for the processing, is
preferable. The example is described in Japanese Patent Application No.
8-222204.
A support of the processing material is not limited, and a plastic film or
paper that are mentioned for light-sensitive materials, can be used. The
thickness of the support is generally 4 .mu.m to 120 .mu.m, preferably 6
to 70 .mu.m. A film to which aluminum is deposited, as described in
Japanese Patent Application No. 8-52586, may be preferably used as well.
As a preferable method for developing the light-sensitive material for use
in the present invention through which shooting has been made, a
color-developing agent built-in-type heat-development system is
preferable, and that is the objective method in view of rapid and easy
processing with a low environmental load. Additionally, an image can be
formed by processing the light-sensitive material of the present invention
by an activator method using an alkaline processing solution, or by a
processing method using a processing solution containing a
color-developing agent/base.
The heating treatment of light-sensitive materials is known in the art, and
the heat-developable light-sensitive materials and the process thereof are
described, for example, in "Shashin Kogaku no Kiso" (published by
Corona-sha, 1970), pages 55 to 555; "Eizo Joho" (published April 1978),
page 40; "Nablettts Handbook of Photography and Reprography," 7th edition
(van Nostrand and Reinhold Company), pages 32 to 33; U.S. Pat. No.
3,152,904, U.S. Pat. No. 3,301,678, U.S. Pat. No. 3,392,020, and U.S. Pat.
No. 3,458,075, GB-1,131,108 and GB-25 1,167,777, and Research Disclosure
(June 1978), pages 9 to 15 (RD-17029).
The activator treatment refers to a treatment wherein a color-developing
agent is built in a light-sensitive material and the light-sensitive
material is developed with a processing solution free from any
color-developing agent. In this case, the processing solution is
characterized in that it does not contain any color-developing agent,
which is normally contained as a development processing solution
component, but the processing solution may contain other components (e.g.
an alkali and an auxiliary developing agent). Examples of the activator
treatment are shown in known publications, such as European Patent Nos.
545,491A1 and 595,165A1.
The method wherein development is carried out using a processing solution
containing a developing agent/base is described in RD. No. 17643, pages 28
to 29; RD. No. 18716, 651, left column to right column; and RD. No.
307105, pages 880 to 881.
Next, the processing materials and processing methods that are used in the
case of heat-development, in the present invention, are hereinafter
explained.
In the present invention, as a method for subjecting to development a
light-sensitive material that has been used for photographing by means of
a camera or the like, preferably a method, wherein the light-sensitive
material and the processing material are put together with the
light-sensitive layer and the processing layer facing each other, in the
presence of water in an amount of 0.1 to 1 times the amount required for
the maximum swelling of all the coating films of the light-sensitive
material and the processing material, except the backing layers, and they
are heated at a temperature of 60 to 100.degree. C. for 5 to 60 sec, is
used.
As a method for providing water, it can be mentioned a method wherein a
light-sensitive material or a processing material are immersed in water,
and then excessive water is removed using a squeeze roller. Furthermore,
as described in JP-A-10-26817, a method for providing water, wherein water
is jetted by water-applying equipment comprising a nozzle with multiple
nozzle holes, to jet water, that are arranged linearly, at a certain
interval, in the direction intersecting with the conveying direction of a
light-sensitive material or a processing material, and an actuator that
serves to dislocate the nozzle toward the light-sensitive material or the
processing material being conveyed, is preferable. The application of
water using a sponge or the like is also preferable.
As a method for heating at the developing steps, a method wherein making
the material contact a block or a plate that is heated, or a method using
a heat roller, a heat drum, an infrared lamp or a far infrared lamp, or
the like can be used as well.
In the present invention, another bleach-fix step, to further remove
developed silver and silver halide remaining in the light-sensitive
material after processing, is not necessary. However, to reduce the load
in reading image information, and to improve image preservability, a
fixing step and/or bleaching step can be provided. In this case, a
conventional liquid treatment can be used, but, it is preferable to
conduct the treatment by a step wherein conducting heat treatment together
with a separate sheet to which a processing agent is applied, as described
in JP-A-9-258402.
In the present invention, when an image is formed based on non-diffusible
dyes, on the light-sensitive material, by performing heat-development in
the presence of a small amount of water, with using the light-sensitive
material containing the coupler and the color-developing agent that
exhibits extremely high stability in the absence of a base, and the
processing material containing a base and/or base precursor, an image
excellent in graininess and sharpness can be obtained; and if output is
carried out based on the thus-obtained image information, onto different
recording materials, such as color paper and a heat-development color
print material, a very excellent color image can be obtained. Also, since
the light-sensitive material is isolated from the base until the
development, rapid development treatment is possible while satisfying high
preservability that is required for materials for photographing.
Further, in contrast to use of a dye-providing compound, use of a colorless
color-developing agent and a coupler is advantageous in the point of
sensitivity, which is an extremely important factor as a material for
photographing.
In the present invention, after the formation of a color-formed image by
heat-development, the remaining silver halide and/or developed silver may
or may not be removed. As a means for outputting to a different material
based on its image information, the generally used projection exposure may
be used, or the image information may be read photoelectrically by
measuring the density of the transmitted light, and its signals may be
outputted. The material to which the output is made may not be
light-sensitive materials and may, for example, be sublimation-type
thermographic (heat sensitive recording) materials, ink jet materials,
electrophotographic materials, and full-color direct thermographic
materials.
An example of a preferable mode in the present invention is one in which,
after the formation of a color-formed image by heat-development, the image
information is read photoelectrically by measuring the transmitted
density, using a CCD image sensor and diffused light, and the information
is transformed into digital signals that in turn are subjected to image
processing and are outputted to a heat-development color printer, such as
"PICTOGRAPHY 3000" (trade name), manufactured by Fuji Photo Film Co., Ltd.
In this case, a good print can be obtained quickly without using any of
the processing solutions used in conventional color photography. Further,
in this case, since the above digital signals can be processed and edited
arbitrarily, the photographed image can be corrected (retouched),
modified, and processed freely, to be outputted.
As image-processing methods that can be preferably applied with using the
light-sensitive material of the present invention, for example, following
methods can be mentioned.
In JP-A-6-139323, an image-processing system and an image-processing method
that can faithfully reproduce a color of the subject from a negative film,
wherein an image of a subject is produced on a color-negative, and then it
is converted to corresponding image data using a scanner or the like, and
the same color as that of the subject is then outputted based on the
demodulated color information, are mentioned, and they can be used in the
present invention.
Further, as an image-processing method wherein graininess and noise of a
digitized image are suppressed and sharpness is enhanced at the same time,
a method to conduct weighting and fractionating treatment to the edge and
noise of an image, based on sharpness enhanced image data, smoothed image
data, and edge detected data, as described in Japanese Patent Application
No. 9-62101; or a method to conduct weighting and fractionating treatment,
with obtaining an edge component from sharpness enhanced image data and
smoothed image data, as described in Japanese Patent Application No.
9-62102, can be used.
Further, to correct variations in color reproducibility in the final print,
which are caused by differences, such as storage condition and processing
condition of photographing materials, with a digital color print system, a
method disclosed in Japanese Patent Application No. 9-59156 can be used,
wherein a patch having four steps or four colors or more is exposed to
light on an unexposed part of a photographic material, and, after
development, the patch density is measured, to obtain a look-up table and
a color conversion matrix required for correction, and thus colors of a
photographic image are corrected by using look-up table conversion or
performing matrix operations.
As a method for converting a color-reproduction range (gamut) of image
data, use can be made of a method wherein, for an image data displayed by
a color signal that is visually recognized to be a neutral color when
values of each color component are made available, the color signal is
divided into components of chromatic colors, and each of them is
individually processed, as described in Japanese Patent Application No.
9-138853.
Furthermore, as a method for removing the deterioration of an image, such
as aberration and lowering of brightness of the edge of the image field
caused by a camera lens, use can be made of an image-processing method and
apparatus that corrects digital image data, wherein a lattice-like
correction pattern to create correction data for the image deterioration
is preliminary recorded on a film, and then after photographing, both the
image and the correction pattern are read out by the film scanner or the
like, to create data to correct deterioration factors caused by the lens
of a camera, and then by using the image-deterioration-correction data,
digital image data is corrected, as described in Japanese Patent
Application No. 9-228160.
Further, with respect to flesh color and sky-blue, if sharpness is
excessively enhanced, graininess (noise) is enhanced simultaneously, and
as a result, it causes an uncomfortable impression, and therefore, it is
preferable to suppress the degree of enhancement of sharpness for flesh
color and sky-blue. As means to attain that, use can be made of a method
wherein, in the sharpness-enhancing processing using unsharp masking
(USM), a USM coefficient is used as functions of (B-A) (R-A), as described
in Japanese Patent Application No. 9-264086.
Further, flesh color, grass-green, and sky-blue are called "Important
Colors" in color reproduction, for which selective color reproducing
processing is required. Among these, with respect to the reproduction of
lightness, it is said that finishing the flesh color to be light, and
sky-blue to be deep, is visually preferable. As a method for reproducing
these important colors so as to have visually preferable brightness, for
example, a method is described in Japanese Patent Application No.
9-346588, wherein a color signal of each picture element is converted
using a coefficient, such as (R-G) or (R-B), which takes a small value if
a corresponding hue is yellow-red, and which takes a large value if the
corresponding hue is cyan blue, and this method can be employed.
Furthermore, as a method for compressing a color signal, use can be made,
for example, of a method described in Japanese Patent Application No.
9-270275, wherein the color signal of each picture element is separated
into a lightness component and a chromaticity component, and, by
selecting, for the chromaticity component, a template having the most
suitable value patterns out of plural hue templates prepared in advance,
hue information is encoded.
To prevent the occurrence of defects, such as color "blind", "attenuation"
of highlight, and "flatness" in a high density area, and the occurrence of
data that is out of a defined region, and at the same time, to conduct
natural enhancing processing, at the time of treatment to increase
saturation, sharpness, or the like, use can be made of an image-processing
method and an image-processing apparatus described in Japanese Patent
Application No. 9-338639, wherein each color density data of color image
data is changed to exposure density data using a characteristic curve, and
image processing, including color enhancement, is performed to
thus-obtained data, and then they are further changed to density data
using a characteristic curve.
The light-sensitive material of the present invention can be used as a
material for photographing or printing. Preferably, it is used as a color
negative film for photographing.
According to the silver halide light-sensitive material of the present
invention, formation of an image with high sensitivity and low fogging can
be achieved both in a simple and quick heat-development treatment and
usual liquid developing treatment.
The present invention will be described in more detail with reference to
the following examples, but the invention should not be construed as being
limited thereto.
EXAMPLES
Example 1
<Preparation Method of Light-sensitive Silver Halide Emulsions>
(1) Preparation of Blue-light-sensitive AgBrI Tabular Grain Emulsion 1B-1
1000 cc of an aqueous solution, containing 1 g of gelatin having an average
molecular weight of 15,000, and 0.9 g of KBr, were stirred, with the
temperature kept at 40.degree. C. To the solution, 17.4 cc of an aqueous
solution (A), containing 0.69 g of AgNO.sub.3, and 17.4 cc of an aqueous
solution (B), containing 0.49 g of KBr, were added simultaneously, over 30
seconds, in a double jet manner. Then, 12 cc of a 10% aqueous solution of
KBr was added to the resulting mixture, and the temperature was elevated
to 75.degree. C. over 27 minutes. After the temperature was raised to
75.degree. C., 35 g of trimellitated gelatin was added to the mixture.
Then, 3 cc of a 0.05% solution of compound (1) was added to the mixture,
and then 115 cc of a 25% aqueous solution (C) of AgNO.sub.3, and 94.2 cc
of a 21.8% aqueous solution (D) of KBr, were simultaneously added, over 25
minutes, with the flow rate being accelerated (the flow rate at the end
was three times that at the start), in a double jet manner. After that,
302 cc of an aqueous solution (E), containing 96.7 g of AgNO.sub.3, and
285 cc of an aqueous solution (F), containing 73.5 g of KBr and 3.5 g of
KI, were simultaneously added to the mixture, over 20 minutes, with the
silver electric potential (to SCE) maintained at -40 mV, and with the flow
rate being accelerated (the flow rate at the end was 5.1 times that at the
start), in a double jet manner. Further, 97 cc of the (C) solution and the
(D) solution were simultaneously added to the mixture, at a constant rate,
for 3 minutes keeping the silver electric potential (to SCE) -40 mV, in a
double jet manner. Then, 1.9 cc of 0.05% solution of sodium
benzenthiosulfonate was added to the mixture.
Then, the temperature of the mixture was lowered to 40.degree. C., and then
an aqueous solution containing 19 g of compound (2), which is an
iodide-ion-releasing agent, was added. To the mixture, 77 cc of a 0.8 M
aqueous solution of sodium sulfite was added, at a constant rate, over 1
minute; the pH was raised to 9 and maintained, to produce iodide ion, and
2 minutes later, the temperature was raised to 55.degree. C. spending 5
minutes, and then the pH was restored to 5.5. Then, after addition of
K.sub.2 IrCl.sub.6, at a rate of 4.times.10.sup.-8 mol/mol-Ag to the total
amount of silver in grains, 200 cc of a solution containing 12 g of
de-ashed gelatin was added. To the mixture, 269 cc of an aqueous solution
(G), containing 68 g of AgNO.sub.3, and 220 cc of an aqueous solution (H),
containing 57 g of KBr, were added simultaneously, at a constant rate,
over 25 minutes.
Then, the resulting emulsion was cooled to 35.degree. C., and, using a
settling agent (1), the emulsion was washed with water by a conventional
flocculation method. Then the pH was raised, 100 g of the gelatin was
added, to disperse the emulsion, and then, pH and pAg were adjusted
respectively to 5.5 and 8.2, to collect the resultant.
By adding compound (3) and water-soluble polymer (1), the pH was adjusted
to 5.5, and the pAg was adjusted to 8.2.
The obtained emulsion was a hexagonal tabular grain emulsion, in which
tabular grains occupied more than 99% of all the projected area of grains,
and the tabular grains were those having an average diameter equivalent to
a sphere of 0.86 .mu.m, an average thickness of 0.12 .mu.m, the average
diameter equivalent to a circle of 1.75 .mu.m, and an aspect ratio of 15.
The iodide content was 5.5 mol %.
By adding a blue-sensitive sensitizing dye (1) (9.5.times.10.sup.-4
mol/mol-Ag), potassium thiocyanate, chloroaurate, sodium thiosulfate, and
mono(pentafuluorophenyl)diphenyl phosphineselenide as a selenium
sensitizer, at 60.degree. C. and under conditions of pH 6.2 and pAg 8.4,
spectral sensitization and chemical sensitization were conducted. To stop
the chemical sensitization, compound (4) was used. The amount of the
chemical sensitizer was adjusted so that 1/100-second exposure sensitivity
of each emulsion became the maximum.
##STR4##
(2) Preparation and Evaluation of a Dispersion and a Coated Sample, and
Preparation of a Dispersion of Zinc Hydroxide to be Used as a Base
Precursor
31 g of zinc hydroxide powder, whose primary particles had a grain size of
0.1 .mu.m, 1.6 g of carboxymethyl cellulose and 0.4 g of sodium
polyacrylate, as a dispersant, 8.5 g of lime-processed ossein gelatin, and
158.5 ml of water were mixed together, and the mixture was dispersed by a
mill containing glass beads for 1 hour. After the dispersion, the glass
beads were filtered off, to obtain 188 g of a dispersion of zinc
hydroxide.
Preparation of Emulsified Dispersion 1 Y of Yellow Coupler
10 g of a yellow coupler YC-1, 8.2 g and 1.6 g of respective developing
agents (1) and (2), 21 g of high-boiling organic solvent (1), and 50.0 ml
of ethyl acetate were dissolved at a temperature of 60.degree. C.
(II-liquid). The resulting solution was mixed with 170 g of an aqueous
solution (I-liquid) comprising 12 g of lime-processed gelatin and 1 g of
surfactant (1), and the mixture was emulsified and dispersed at 10,000 rpm
for 20 minutes using a dissolver stirrer. After the dispersion, distilled
water was added to bring the total weight to 300 g, and they were mixed at
2000 rpm for 10 minutes.
##STR5##
By adding N-3 to the emulsion 1B-1, and then adding an emulsified
dispersion 1 Y, a light-sensitive emulsion coating solution was prepared.
The solution was coated, together with the gelatin dispersion of zinc
hydroxide, on a support with a composition shown in Table 1, to prepare
Sample 101.
TABLE 1
______________________________________
Light-sensitive material 101
Layer Added amount
Composition Added material (mg/m.sup.2)
______________________________________
Protective layer
Acid-processed gelatin
1000
Matting agent (silica) 50
Surfactant (2) 100
Surfactant (3) 300
Water-soluble polymer (1) 15
Hardener (1) 35
Interlayer Lime-processed gelatin 950
Surfactant (3) 15
Zinc hydroxide 1100
Water-soluble polymer (1) 15
Yellow color- Lime-processed gelatin 800
forming Emulsion 1B-1 1931
layer (in terms
of silver)
Yellow coupler YC-(1) 524
Developing agent (1) 421
Developing agent (2) 85
Surfactant (1) 19
High-boiling organic solvent (1) 1061
Water-soluble polymer (1) 14
Transparent PET base (120 .mu.m),
both sides of which is coated with a gelatin subbing layer
Antistatic layer
Lime-processed gelatin (molecular
60
weight 12000)
Fine grains of a composite of stannic 180
oxide-antimony oxide having an
average grain diameter of 0.005 .mu.m
(secondary aggregation grain
diameter of about 0.08 .mu.m at the
specific resistance of 5.OMEGA. .multidot. cm.sup.2)
Polyethylene-p-nonyiphenot 5
(polymerization degree: 10)
Backing second Lime-processed gelatin (molecular 2000
layer weight 12000)
Surfactant (3) 11
PMMA latex (diameter: 6 .mu.m) 9
Hardener (2) 455
Backing third Methyl methacrylate/styrene/2- 1000
layer ethythexyl acrytate/methacrylic acid
copolymer
Surfactant (3) 1.5
Surfactant (4) 20
Surfactant (5) 2.5
Surfactant (2)
#STR6##
- Surfactant (3)
#STR7##
- Surfactant (4)
#STR8##
- Surfactant (5)
#STR9##
- Hardener (1)
(CH.sub.2 .dbd.CHSO.sub.2).sub.2 --CH.sub.2
______________________________________
Samples 101 to 114 were prepared by adding, to the emulsion 1B-1, a
nitrogen-containing heterocyclic compound, in combination with zinc
nitrate, as shown below.
In Samples 104 to 108, the nitrogen-containing heterocyclic compound and
zinc nitrate were added to the light-sensitive emulsion coating solution.
In Sample 103, N-18 was prepared in accordance with methods disclosed in
the working example of U.S. Pat. No. 3,649,267 or JP-A-62-291642, and zinc
ion was not added thereto. In Sample 109, N-3 was added to II-liquid, and
zinc ion was added to I-liquid at the preparation of 1 Y. Sample 110 was
prepared by using a mixture, which was obtained by adding an alkaline
aqueous solution of N-3, to a 4% aqueous gelatin solution containing zinc
ion that was well-stirred at 40.degree. C., and then stirring for 10
minutes.
______________________________________
Additives (mol)
______________________________________
101 (Comparative
N-3 (8 .times. 10.sup.-3)
Blank
example)
102 (Comparative Blank Blank
example)
103 (Comparative N-18 (8 .times. 10.sup.-3) Zinc ion (4 .times.
10.sup.-3 :
example) exist in complex)
104 (Comparative Blank Zinc ion (2 .times. 10.sup.-2)
example)
105 (Comparative N-3 (8 .times. 10.sup.-3) Zinc ion (6 .times. 10.sup.-3
)
example)
106 (This N-3 (8 .times. 10.sup.-3) Zinc ion (8 .times. 10.sup.-3)
invention)
107 (This N-3 (8 .times. 10.sup.-3) Zinc ion (1 .times. 10.sup.-2)
invention)
108 (This N-3 (8 .times. 10.sup.-3) Zinc ion (2 .times. 10.sup.-2)
invention)
109 (This N-3 (8 .times. 10.sup.-3) Zinc ion (2 .times. 10.sup.-2)
invention)
110 (This N-3 (8 .times. 10.sup.-3) Zinc ion (2 .times. 10.sup.-2)
invention)
111 (Comparative N-3 (8 .times. 10.sup.-3) Calcium ion (2 .times.
10.sup.-2)
example)
112 (Comparative N-3 (8 .times. 10.sup.-3) Cadmium ion (2 .times.
10.sup.-2)
example)
113 (Comparative Blank Calcium ion (2 .times. 10.sup.-2)
example)
114 (Comparative Blank Cadmium ion (2 .times. 10.sup.-2)
example)
______________________________________
These light-sensitive materials were exposed to light at 500 lux for 1/100
second, through an optical wedge, blue filter BPN42, manufactured by Fuji
Photo Film Co., Ltd., and a 4800K color conversion filter.
Warm water at 40.degree. C. was applied to each of the exposed
light-sensitive materials, in an amount of 15 ml/m.sup.2 ; the film
surfaces of the light-sensitive material and the processing material P-1
were overlapped with each other, and they were heat-developed at
83.degree. C. for 17 sec using a heat drum. Further, the film surfaces of
the light-sensitive material and the processing material P-2 were
overlapped with each other, and they were processed for 20 seconds at a
temperature of 50.degree. C. using a heat drum; and when they were peeled
off, a yellow color wedge-like image was obtained.
The composition of the processing material P-1 is shown in Tables 2 and 3.
The composition of the processing material P-2 is shown in Table 4.
TABLE 2
______________________________________
P-1
Layer Added amount
Composition Added material (mg/m.sup.2)
______________________________________
Fourth layer
Lime-processed gelatin
220
Protective Water-soluble polymer (2) 60
layer Water-soluble polymer (3) 200
Potassium nitrate 12
PMMA latex (diameter: 6 .mu.m) 10
Surfactant (3) 7
Surfactant (4) 7
Surfactant (5) 10
Third layer Lime-processed gelatin 240
Interlayer Water-soluble polymer (2) 24
Hardener (2) 180
Surfactant (3) 9
Second layer Lime-processed gelatin 2400
Base- Water-soluble polymer (3) 360
producing Water-soluble polymer (4) 700
layer Water-soluble polymer (5) 1000
Guanidine pocolinate 2910
Potassium quinolinate 225
Sodium quinolinate 180
Surfactant (3) 24
First layer Lime-processed gelatin 280
Interlayer Water-soluble polymer (2) 12
Subbig layer Surfactant (3) 14
Hardener (2) 185
Transparent base A (43 .mu.m)
______________________________________
TABLE 3
______________________________________
Composition of Base A
Added
amount
Name of layer Composition (mg/m.sup.2)
______________________________________
Subbing layer of
Lime-processed gelatin
100
surface
Polymer layer Polyethylene 62500
terephthalate
Subbing layer of Polymer (Methyl 1000
back surface methacrylate/styrene/2-
ethylhexyl
acrylate/methacrylic
acid copolymer)
PMMA latex 120
______________________________________
TABLE 4
______________________________________
P-2
Layer Added amount
Composition Added material (mg/m.sup.2)
______________________________________
Fourth layer
Lime-processed gelatin
220
Protective Water-soluble polymer (2) 60
layer Water-soluble polymer (3) 200
Potassium nitrate 12
PMMA latex (diameter: 6 .mu.m) 10
Surfactant (3) 7
Surfactant (4) 7
Surfactant (5) 10
Third layer Lime-processed gelatin 240
Interlayer Water-soluble polymer (2) 24
Hardener (2) 180
Surfactant (3) 9
Second layer Lime-processed gelatin 2400
Fixing agent Silver halide solvent (1) 5500
layer Water-soluble polymer (5) 2000
Surfactant (3) 24
First layer Lime-processed gelatin 280
Interlayer Water-soluble polymer (2) 12
Subbing layer Surfactant (3) 14
Hardener (2) 185
Transparent base A (43 .mu.m) (the same base as to P-1)
______________________________________
Water-soluble polymer (2)
.kappa.--Carrageenan
Water-soluble polymer (3)
Sumika Gel L-5H (trade name, manufactured by Sumitomo Chemical Co., Ltd.)
Hardener (2)
##STR10##
Water-soluble polymer (4)
Dextran (molecular weight of 70,000)
Water-soluble polymer (5)
##STR11##
Silver halide solvent (1)
##STR12##
Further, for the above samples, the same exposure was conducted, and then
they were processed using a conventional processing bath (processing bath
CN-16 for color negative film (trade name)) containing a color-developing
agent, at 38.degree. C., for 165 seconds. The transmission density of each
of the color-formed samples obtained by heat-development and
color-development processing was measured using a blue filter, and a
so-called "characteristic curve" was obtained. The relative sensitivity
was determined as follows: the sensitivity was obtained from the
reciprocal of the exposure amount giving a density that is 0.15 higher
than the density of fog, and the sensitivity found was shown in terms of
relative value by assuming the value of Sample 101 that was heat-developed
to be 100. The results are shown in Table 5, together with Dmin.
TABLE 5
__________________________________________________________________________
Divalent cation/
nitrogen
containing-
heterocyclic
compound Heat-development CN-16
(molar ratio)
Sensitivity
Dmin
Sensitivity
Dmin
__________________________________________________________________________
101 (Comparative example)
0 100 0.3 56 0.15
102 (Comparative example) -- -- 1.16 102 0.31
103 (Comparative example) 0.5 98 0.32 60 0.12
104 (Comparative example) -- -- 1.21 105 0.3
105 (Comparative example) 0.75 99 0.31 81 0.13
106 (This invention) 1 102 0.32 95 0.27
107 (This invention) 1.25 102 0.29 97 0.26
108 (This invention) 2.5 105 0.31 102 0.25
109 (This invention) 2.5 102 0.29 105 0.26
110 (This invention) 2.5 102 0.28 105 0.27
111 (Comparative example) 2.5 100 0.32 50 0.11
112 (Comparative example) 2.5 107 0.35 59 0.12
113 (Comparative example) -- -- 1.37 100 0.31
114 (Comparative example) -- -- 1.42 105 0.42
__________________________________________________________________________
From these results, it is understood that high sensitivity and a low Dmin
were attained in both heat-development and the CN-16 processing, when the
divalent metal cation for use in the present invention, which is an acid
having intermediate hardness/softness in accordance with the HSAB
principle, existed in amounts equimolar or more to the nitrogen-containing
heterocyclic compound for use in the present invention. Further, to form
complex of the divalent metal cation and the nitrogen-containing
heterocyclic compound for use in the present invention was also
preferable.
Example 2
Samples 201 to 216 were prepared in same manner as in Example 1, by
combining the emulsion 1B-1 with the nitrogen-containing compound and the
divalent metal cation as shown below. In Sample 205, N-42 was prepared
according to the working example in U.S. Pat. No. 3,649,267 or
JP-A-62-291642, and zinc ion was not added thereto. In Samples 205 to 209,
the nitrogen-containing heterocyclic compound and zinc nitrate were added
to the light-sensitive emulsion coating solution. Sample 210 was prepared
using a mixture, which was obtained by adding an alkaline aqueous solution
of N-25, to a 4% aqueous gelatin solution containing zinc ion that was
well-stirred at 40.degree. C., and then stirring for 10 minutes. Sample
211 was prepared by additionally adding nitrate ion to the light-sensitive
emulsion coating solution of Sample 210. In Samples 212 to 213, the
nitrogen-containing heterocyclic compounds and zinc nitrate were added to
the light-sensitive emulsion coating solution. Sample 214 was prepared
using a gelatin dispersion of zinc salt of N-25, which is prepared using
equimolar amounts of zinc ion and N-25 that was prepared in Sample 210,
and by adding N-3 and remaining zinc ion to the light-sensitive emulsion
coating solution.
______________________________________
Additives (mol)
______________________________________
201 (Comparative example)
Benzotriazole (8 .times. 10.sup.-3); Blank
202 (Comparative example) N-28 (2 .times. 10.sup.-3); Blank
203 (Comparative example) N-25 (2 .times. 10.sup.-3); Blank
204 (Comparative example) Phenylmercaptotetrazole
(2 .times. 10.sup.-3); Blank
205 (Comparative example) N-42 (2 .times. 10.sup.-3); Zinc ion (10.sup.-
3)
(in complex)
206 (Comparative example) Benzotriazole (8 .times. 10.sup.-3); Zinc
ion (2 .times. 10.sup.-2)
207 (Comparative example) Phenylmercaptotetrazole
(2 .times. 10.sup.-3); Zinc ion (2 .times. 10.sup.-3)
208 (This invention) N-28 (2 .times. 10.sup.-3); Zinc ion
(2 .times. 10.sup.-3)
209 (This invention) N-25 (2 .times. 10.sup.-3); Zinc ion
(2 .times. 10.sup.-3)
210 (This invention) N-25 (2 .times. 10.sup.-3); Zinc ion
(2 .times. 10.sup.-3)
211 (This invention) N-25 (8 .times. 10.sup.-3); Zinc ion
(2 .times. 10.sup.-2)
212 (This invention) N-25 (2 .times. 10.sup.-3), N-3 (8 .times.
10.sup.-3);
Zinc ion (2 .times. 10.sup.-2)
213 (This invention) N-28 (2 .times. 10.sup.-3), N-3 (8 .times.
10.sup.-3);
Zinc ion (2 .times. 10.sup.-2)
214 (This invention) N-25 (2 .times. 10.sup.-3), N-3 (8 .times.
10.sup.-3);
Zinc ion (2 .times. 10.sup.-2)
215 (Comparative example) N-25 (2 .times. 10.sup.-3), N-3 (8 .times.
10.sup.-3);
Blank
216 (Comparative example) N-28 (2 .times. 10.sup.-3), N-3 (8 .times.
10.sup.-3);
Blank
______________________________________
These samples were exposed and developed in the same manner as in Example
1, then sensitivity and minimum color density (Dmin) were obtained, and
the results are shown in Table 6. The sensitivity was represented in terms
of relative value by assuming the value of Sample 101 that was
heat-developed to be 100.
TABLE 6
__________________________________________________________________________
Divalent cation/
nitrogen
containing-
heterocyclic
compound Heat-development CN-16
(molar ratio)
Sensitivity
Dmin
Sensitivity
Dmin
__________________________________________________________________________
101 (Comparative example)
0 100 0.3 56 0.15
201 (Comparative example) 0 46 0.85 85 0.27
202 (Comparative example) 0 52 0.72 42 0.16
203 (Comparative example) 0 36 0.89 45 0.12
204 (Comparative example) 0 31 0.86 65 0.22
205 (Comparative example) 0.5 56 0.92 71 0.27
102 (Comparative example) -- -- 1.16 102 0.31
104 (Comparative example) -- -- 1.21 105 0.3
107 (This invention) 2.5 105 0.31 102 0.25
206 (Comparative example) 2.5 48 0.91 71 0.27
207 (Comparative example) 1 42 0.97 74 0.23
208 (This invention) 1 105 0.48 97 0.26
209 (This invention) 1 103 0.51 100 0.31
210 (This invention) 1 102 0.51 102 0.28
211 (This invention) 2.5 102 0.5 105 0.27
212 (This invention) 2 110 0.21 98 0.26
213 (This invention) 2 112 0.23 101 0.27
214 (This invention) 2 115 0.22 102 0.28
215 (Comparative example) -- 115 0.22 43 0.19
216 (Comparative example) -- 117 0.21 46 0.21
__________________________________________________________________________
The results of Table 6 show that the use of the highly oil-soluble
nitrogen-containing heterocyclic compound for use in the present invention
give advantages. Further, the combination use of a phenylazole compound
having a mercapto group and a benzotriazole compound is also preferable,
in view of high sensitivity and of low Dmin.
Example 3
The method for preparing blue-light-sensitive {111} high-silver-chloride
tabular grain emulsion 2B-1 is described.
1200 ml of a gelatin aqueous solution containing 2.1 g of deionized
alkali-processed bone gelatin and 2 g of sodium chloride, was put into a
reaction vessel and was maintained at 35.degree. C. While the solution was
strongly stirred, as the first step, to the solution, 60 ml of (A)-liquid,
containing 7.2 g of silver nitrate, and 60 ml of (B)-liquid, containing
2.6 g of sodium chloride, were simultaneously added and mixed over one
minute. One minute after the completion of addition, 40 ml of (C)-liquid,
which is 80 ml of an aqueous solution containing 0.494 g of a
crystal-habit-controlling agent (1), was added to the mixture, and, one
minute later, 60 ml of a 10% aqueous solution of sodium chloride was
added. After that, the mixture was heated to 75.degree. C. spending 50
minutes, and, 10 minutes later, 450 ml of aqueous gelatin solution,
containing 45 g of phthalated gelatin, was added, and 40 ml of the
(C)-liquid was added to the mixture 3 minutes later. In addition, one
minute later, 768 ml of (D)-liquid, which is an aqueous solution
containing 113 g of silver nitrate, and 786 ml of (E)-liquid, which is an
aqueous solution containing 31.5 g of sodium chloride and 20 g of
potassium bromide, were added, simultaneously, at an initial rate of 2.85
ml/min, and at an accelerated rate of 0.818 ml/min.sup.2. 5 minutes before
the completion of addition of the (D)- and (E)-liquids, 30 ml of
(F)-liquid, containing 0.43 g of sodium chloride, 0.015 g of yellow
prussiate of potash, and 0.72 g of potassium iodide, was added, spending 5
minutes. Further, 4 minutes before the completion of the addition of the
(D)- and (E)-liquids, 34 ml of a 10% aqueous solution of potassium bromide
was added, in 3 seconds. 3 minutes after the completion of the addition of
the (D)- and (E)-liquids, 159 cc of a 2 mM solution (water:methanol=1:1)
of blue-sensitive sensitizing dye (2) was added and maintained for 10
minutes. The temperature of the mixture was lowered to 50.degree. C., and
desalting was carried out using a settling agent (2), in accordance with a
conventional method. The dispersion was made by using 67 g of deionized
alkali-processed bone gelatin, 30 cc of a 2% aqueous solution of
Zn(NO.sub.3).sub.2.6H.sub.2 O (zinc nitrate) (3.times.10.sup.-3 mole per
one mole of silver), compound (3), phenoxyethanol, and water-soluble
polymer (1). The mixture was adjusted to pH 6.3, and pAg 7.7.
The obtained emulsion comprised {111} tabular grains of silver
chlorobromide, having an average grain size represented by a diameter for
a corresponding sphere of 0.93 .mu.m, an average thickness of 0.12 .mu.m,
an average diameter equivalent to a circle of 2.1 .mu.m, an average aspect
ratio of 17, and a content of silver bromide of 29 mol %.
Chemical sensitization was carried out at a temperature of 60.degree. C. by
sequentially adding compound (5),
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, sodium thiosulfate,
mono(pentafluorophenyl)diphenylphosphine selenide, being a selenium
sensitizer; chloroaurate, and sodium benzenethiosulfonate, to the
emulsion, to achieve the maximum sensitivity. 15 minutes before the end of
the chemical sensitization, 80 cc of a 2 mM (methanol:water=1:1) solution
of blue-sensitive sensitizing dye (2) was added. Stopping of the chemical
sensitization was done using compound (5).
Blue-sensitive sensitizing dye (2)
##STR13##
Crystal habit controlling agent (1)
##STR14##
Settling agent (2)
##STR15##
Compound (5)
##STR16##
The light-sensitive material 301 was prepared in the same manner as the
light-sensitive material 213, except that the emulsion 1B-1 was changed to
2B-1.
The exposure and development carried out for this material 301, in the same
manner as in Example 1, and the material showed high sensitivity and low
fogging in heat-development and CN-16 processing.
Example 4
Preparation of Red-light-sensitive AgBrI Tabular Grain Emulsion 4R-1
The AgBrI tabular grain emulsion 4R-1 was prepared in the same manner as
for the AgBrI tabular grain emulsion 1B-1, except that compound (1) was
not added, the aqueous solution (H) was changed to 220 cc of a liquid
containing 48 g of KBr and 110 mg of yellow prussiate of potash; and then,
90 cc of 10% solution of KBr was added; zinc nitrate was added, at
1.times.10.sup.-3 mol/mol-Ag for the total silver amount of grains, at the
time of gelatin dispersion, and the sensitizing dye was changed to the
same molar quantity of red-light-sensitizing dyes, with the ratio of the
red-light-sensitive sensitizing dyes (1), (2), and (3) being 61:2:33
(molar ratio). The obtained emulsion was a hexagonal tabular grain
emulsion, in which tabular grains occupied more than 99% of all projected
area of all grains, and the tabular grains had an average diameter
corresponding to a sphere of 0.86 .mu.m, an average thickness of 0.12
.mu.m, an average diameter equivalent to a circle of 1.75 .mu.m, and an
average aspect ratio of 15. The content of iodide was 5.5 mol %.
Red-sensitive sensitizing dye (1)
##STR17##
Red-sensitive sensitizing dye (2)
##STR18##
Red-sensitive sensitizing dye (3)
##STR19##
Preparation of Emulsified Dispersion 4Cy of Cyan Coupler
10.7 g of a cyan coupler CC-(1), 8.2 g and 1.05 g of respective developing
agents (3) and (2), 11 g of high-boiling organic solvent (1), and 24.0 ml
of ethyl acetate were dissolved at a temperature of 60.degree. C. 8 g of
high-boiling organic solvent (1) and 50.0 ml of ethyl acetate were
dissolved at 60.degree. C. (II-liquid). The resulting solution was mixed
with 170 g of an aqueous solution (I-liquid) comprising 12 g of
lime-processed gelatin and 1 g of surfactant (1), and the mixture was
emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver
stirrer. After the dispersion, distilled water was added to bring the
total weight to 300 g, and they were mixed at 2000 rpm for 10 minutes.
Cyan coupler
CC-(1)
##STR20##
Developing agent-(3)
##STR21##
Samples 401 to 403, which are single-layer color photographic materials,
were prepared in the same manner and the same composition as Sample 101,
except that the above emulsion 4R-1 and the above cyan coupler emulsified
dispersion 4 Cy were used in place of emulsion 1B-1 and yellow coupler
emulsified dispersion 1 Y, with the combination of the nitrogen-containing
heterocyclic compound and zinc ion as shown below, together with gelatin
solution containing zinc hydroxide.
______________________________________
Additives (mol)
______________________________________
401 (Comparative example)
N-3 (3 .times. 10.sup.-3), N-25 (10.sup.-3);
Zinc ion (10.sup.-3)
402 (Comparative example) Blank; Zinc ion (1 .times. 10.sup.-2)
403 (This invention) N-3 (3 .times. 10.sup.-3), N-25
(10.sup.-3);
Zinc ion (1 .times. 10.sup.-2)
______________________________________
The zinc ion used in Sample 401 means the zinc ion added when the emulsion
was dispersed into the gelatin.
For Samples 401 to 403, exposure to light, development processing, and
measurement of sensitivity and minimum color density (Dmin) were conducted
in the same manner as in Example 1, except that the BPN42 optical filter
used at the time of exposure was changed to a red filter SC60,
manufactured by Fuji Photo Film Co., Ltd., and the transmission density in
the color-developed samples were measured with the red filter. The results
are shown in Table 7. The sensitivity was represented by a relative value
with the value obtained by heat-development of sample 401 assumed to be
100.
TABLE 7
__________________________________________________________________________
Divalent cation/
nitrogen
containing-
heterocyclic
compound Heat-development CN-16
(molar ratio)
Sensitivity
Dmin
Sensitivity
Dmin
__________________________________________________________________________
401 (Comparative example)
0.25 100 0.32
56 0.15
402 (Comparative example) -- 78 0.79 100 0.32
403 (This invention) 2.5 102 0.33 105 0.18
__________________________________________________________________________
Example 5
Preparation of Green-light-sensitive AgBrI Tabular Grain Emulsion 5G-1
The AgBrI tabular grain emulsion 5G-1 was prepared in the same manner as
for the AgBrI tabular grain emulsion 4R-1, except that the sensitizing
dyes were changed to the same molar quantity of the
green-light-sensitizing dyes, with the ratio of the green-light-sensitive
sensitizing dyes (1), (2), and (3) being 70:20:10 (molar ratio). The
obtained emulsion was a hexagonal tabular grain emulsion, in which tabular
grains occupied more than 99% of all projected area of all grains, and the
tabular grains had an average diameter corresponding-to a sphere of 0.86
.mu.m, an average thickness of 0.12 .mu.m, an average diameter equivalent
to a circle of 1.75 .mu.m, and an average aspect ratio of 15. The content
of iodide was 5.5 mol %.
Green-sensitive sensitizing dye (1)
##STR22##
Green-sensitive sensitizing dye (2)
##STR23##
Green-sensitive sensitizing dye (3)
##STR24##
Preparation of Emulsified Dispersion 5M of Magenta Coupler
7.5 g and 1 g of magenta couplers MC-(1) and MC-(2) respectively, 8.2 g and
1.05 g of respective developing agents (3) and (2), 11 g of high-boiling
organic solvent (1), and 24.0 ml of ethyl acetate were dissolved at a
temperature of 60.degree. C. 8 g of high-boiling organic solvent (1) and
50.0 ml of ethyl acetate were dissolved at 60.degree. C. (II-liquid). The
resulting solution was mixed with 170 g of an aqueous solution (I-liquid)
comprising 12 g of lime-processed gelatin and 1 g of surfactant (1), and
the mixture was emulsified and dispersed at 10,000 rpm for 20 minutes
using a dissolver stirrer. After the dispersion, distilled water was added
to bring the total weight to 300 g, and they were mixed at 2000 rpm for 10
minutes.
##STR25##
Samples 501 to 503, which are single layer color photographic materials,
were prepared in the same manner and the same composition as Sample 101,
except that the above emulsion 5G-1 and the above magenta coupler
emulsified dispersion 5M were used in place of emulsion 1B-1 and yellow
coupler emulsified dispersion 1 Y, with the combination of the
nitrogen-containing heterocyclic compound and zinc ion as shown below,
together with gelatin solution containing zinc hydroxide.
______________________________________
Additives (mol)
______________________________________
501 (Comparative example)
N-3 (1 .times. 10.sup.-3), N-25 (10.sup.-3);
Zinc ion (10.sup.-3)
502 (Comparative example) Blank; Zinc ion (2 .times. 10.sup.-2)
503 (This invention) N-3 (1 .times. 10.sup.-3), N-25
(10.sup.-3);
Zinc ion (5 .times. 10.sup.-3)
______________________________________
The zinc ion used in Sample 501 means the zinc ion added when the emulsion
was dispersed into the gelatin.
For the samples, exposure to light, development processing, and measurement
of sensitivity and minimum color density (Dmin) were conducted in the same
manner as in Example 1, except that the BPN42 optical filter used at the
time of exposure was changed to a red filter SC50, manufactured by Fuji
Photo Film Co., Ltd., and the transmission density in the color-developed
samples were measured with the green filter. The results are shown in
Table 8. The sensitivity was represented by a relative value with the
value obtained by heat-development of sample 501 assumed to be 100.
TABLE 8
__________________________________________________________________________
Divalent cation/
nitrogen
containing-
heterocyclic
compound Heat-development CN-16
(molar ratio)
Sensitivity
Dmin
Sensitivity
Dmin
__________________________________________________________________________
501 (Comparative example)
0.5 100 0.25
41 0.11
502 (Comparative example) -- 65 0.86 97 0.22
503 (This invention) 2.5 102 0.24 100 0.19
__________________________________________________________________________
Example 6
By methods shown below, a multilayer full-color photographic
light-sensitive material was prepared. Preparation of
green-light-sensitive AgBrI tabular grain emulsion 6G-1.
The emulsion 4-B in Example 6 of JP-A-10-1612263 or in Example 6 of
EP-A-0845706A2 was used as an emulsion 6G-1. The obtained emulsion was a
hexagonal tabular grain emulsion, in which tabular grains occupied more
than 99% of all projected area of all grains, and the tabular grains had
an average diameter corresponding to a sphere of 0.66 .mu.m, an average
thickness of 0.095 .mu.m, an average diameter equivalent to a circle of
1.4 .mu.m, and an average aspect ratio of 14.5.
Preparation of Green-light-sensitive AgBrI Tabular Grain Emulsion 6G-2
The emulsion 4-D in Example 6 of JP-A-10-1612263 or in Example 6 of
EP-A-0845706A2 was used as an emulsion 6G-2. The obtained emulsion was a
hexagonal tabular grain emulsion, in which tabular grains occupied more
than 99% of all projected area of all grains, and the tabular grains had
an average diameter corresponding to a sphere of 0.37 .mu.m, an average
thickness of 0.1 .mu.m, an average diameter equivalent to a circle of 0.58
.mu.m, and an average aspect ratio of 5.8.
Preparation of Red-light-sensitive AgBrI Tabular Grain Emulsion 6R-1
The AgBrI tabular grain emulsion 6R-1 was prepared in the same manner as in
the green-light-sensitive AgBrI tabular grain emulsion 6G-1, except that
the sensitizing dye was changed to the same molar quantity of
red-light-sensitizing dyes, with the ratio of the red-light-sensitive
sensitizing dyes (1), (2), and (3) being 58:2:40 (molar ratio).
Preparation of Red-light-sensitive AgBrI Tabular Grain Emulsion 6R-2
The AgBrI tabular grain emulsion 6R-2 was prepared in the same manner as in
the green-light-sensitive AgBrI tabular grain emulsion 6G-2, except that
the sensitizing dye was changed to the same molar quantity of
red-light-sensitizing dyes, with the ratio of the red-light-sensitive
sensitizing dyes (1), (2), and (3) being 58:2:40 (molar ratio).
Preparation of Blue-light-sensitive AgBrI Tabular Grain Emulsion 6B-1
The AgBrI tabular grain emulsion 6B-1 was prepared in the same manner as in
the green-light-sensitive AgBrI tabular grain emulsion 6G-1, except that
the sensitizing dye was changed to the same molar quantity of
blue-light-sensitizing dye (1).
Preparation of Blue-light-sensitive AgBrI Tabular Grain Emulsion 6B-2
The AgBrI tabular grain emulsion 6B-2 was prepared in the same manner as in
the green-light-sensitive AgBrI tabular grain emulsion 6G-2, except that
the sensitizing dye was changed to the same molar quantity of
blue-light-sensitizing dye (1).
To each emulsion was added zinc nitrate, at 1.times.10.sup.-3 mole per one
mole of silver for the total silver amount of grains.
<Preparation of Dye Compositions for Yellow Filter, Magenta Filter, and
Antihalation Layer>
The yellow filter dye was prepared as an emulsified dispersion in the
following manner.
14 g of YF-1 and 13 g of a high-boiling organic solvent (2) were weighed,
and ethyl acetate was added thereto, and the mixture was heated to about
60.degree. C. and dissolved, to make a uniform solution. To 100 cc of this
solution, 1.0 g of a surface active agent (1), and 190 cc of a 6.6%
aqueous solution of lime-processed gelatin heated to about 60.degree. C.,
were added, and the mixture was dispersed by a homogenizer for 10 minutes
at 10,000 rpm.
The magenta filter dye was prepared as an emulsified dispersion in the
following manner.
13 g of MF-1 and 13 g of a high-boiling organic solvent (2) were weighed,
and ethyl acetate was added thereto, and the mixture was heated to about
60.degree. C. and dissolved, to make a uniform solution. To 100 cc of this
solution, 1.0 g of a surface active agent (1) and 190 cc of 6.6% aqueous
solution of lime-processed gelatin heated to about 60.degree. C. were
added, and the mixture was dispersed by a homogenizer for 10 minutes at
10,000 rpm.
The cyan filter dye for antihalation layer was prepared as an emulsified
dispersion in the following manner.
20 g of CF-1 and 15 g of a high-boiling organic solvent (2) were weighed,
and ethyl acetate was added thereto, and the mixture was heated to about
60.degree. C. and dissolved, to make a uniform solution. To 100 cc of this
solution, 1.0 g of a surface active agent (1) and 190 cc of 6.6% aqueous
solution of lime-processed gelatin heated to about 60.degree. C. were
added, and the mixture was dispersed by a homogenizer for 10 minutes at
10,000 rpm.
##STR26##
<Preparation of Support>
The same support as in Example of 6 of JP-A-10-161263 or Example 6 of
EP-0845706A2 was used.
A multilayer light-sensitive material 602 according to the present
invention was prepared, by using the blue-light-sensitive emulsions 1B-1,
6B-1, and 4B-2, and yellow coupler gelatin dispersion 1 Y, for a blue
light-sensitive layer; the green-light-sensitive emulsions 5G-1, 6G-1, and
6G-2, and the magenta coupler gelatin dispersion 5M, for a green
light-sensitive layer; the red light-sensitive emulsions 4R-1, 6R-1, and
6R-2, and cyan coupler gelatin dispersion 4 Cy, for a red light-sensitive
layer; three kinds of dye dispersions, the zinc hydroxide dispersion, and
a support. The nitrogen-containing heterocyclic compound N-3 was added to
the coupler emulsified dispersion. The nitrogen-containing heterocyclic
compound N-25 was added as the gelatin dispersion of the complex with zinc
ion, which was prepared in Sample 210 in Example 2. The remaining zinc ion
was additionally added when the coating solution was prepared.
A light-sensitive material 602, as a comparative example, was prepared in
the same manner as for the light-sensitive material 601, except that N-25
was added in the form of a methanol solution, and zinc ion of the coating
solution was not added thereto.
TABLE 9
__________________________________________________________________________
Light-sensitive material 601
Layer Added amount
Composition
Added material (mg/m.sup.2)
(.mu.mol/m.sup.2)
__________________________________________________________________________
Protective
Acid-processed gelatin
1000
layer Matting agent (silica) 100
Surfactant (5) 100
Surfactant (3) 300
Water-soluble polymer (1) 20
Interlayer Lime-processed gelatin 500
Surfactant (3) 15
Zinc hydroxide 340
Water-soluble polymer (1) 30
Yellow color- Lime-processed gelatin 1184
forming Emulsion 1B-1 500 4634
layer (high- (in terms of silver)
sensitivity Nitrogen-containing compound N-3 8.4 32
layer) Nitrogen-containing compound N-25 1.6 5.3
Zinc hydroxide .multidot. 6H.sub.2 O 19.3 65
Yellow coupler YC-(1) 228
Developing agent (1) 185
Developing agent (2) 38
Surfactant (1) 26
High-boiling Organic solvent (1) 466
Water-soluble polymer (1) 15
Yellow Lime-processed gelatin 1725
color- Emulsion 6B-1 320 2966
forming layer Emulsion 6B-2 180 1668
(low- (in terms of silver)
sensitivity Nitrogen-containing compound N-3 15.7 60
layer) Nitrogen-containing compound N-25 3.926 13
Zinc hydroxide .multidot. 6H.sub.2 O 74.25 250
Yellow coupler YC-(1) 357
Developing agent (1) 290
Developing agent (2) 59
Surfactant (1) 42
High-boiling organic solvent (1) 731
Water-soluble polymer (1) 43
Interlayer Lime-processed gelatin 210
Yellow filter Yellow dye YF-1 140
High-boiling organic solvent (2) 130
Hardener (1) 130
Magenta Lime-processed gelatin 496
color- Emulsion 5G-1 721 6682
forming (in terms of silver)
layer (high- Nitrogen-containing compound N-3 1.1 4.2
sensitivity Nitrogen-containing compound N-25 1.87 6.2
layer) Zinc hydroxide .multidot. 6H.sub.2 O 5.64 19
Magenta coupler MC-(1) 62
Magenta coupler MC-(2) 8
Developing agent (3) 68
Developing agent (2) 8.7
Surfactant (1) 6.5
High-boiling organic solvent (1) 66
Water-soluble polymer (1) 15
Magenta Lime-processed gelatin 551
color-forming Emulsion 6G-1 346 3207
layer (in terms of silver)
(medium- Nitrogen-containing compound N-3 1.5 5.8
sensitivity Nitrogen-containing compound N-25 1.54 5.1
layer) Zinc hydroxide .multidot. 6H.sub.2 O 5.05 17
Magenta coupler MC-(1) 100
Magenta coupler MC-(2) 15
Developing agent (3) 109
Developing agent (2) 14
Surfactant (1) 11
High-boiling organic solvent (1) 107
Water-soluble polymer (1) 3
Magenta Lime-processed gelatin 665
color-forming Emulsion 6G-2 300 2780
layer (low- (in terms of silver)
sensitivity Nitrogen-containing compound N-3 3.7 14
layer) Nitrogen-containing compound N-25 1.27 4.2
Zinc hydroxide .multidot. 6H.sub.2 O 5.05 17
Magenta coupler MC-(1) 274
Magenta coupler MC-(2) 36.5
Developing agent (3) 300
Developing agent (2) 38.5
Surfactant (1) 28
High-boiling organic solvent (1) 292
Water-soluble polymer (1) 5
Interlayer Lime-processed gelatin 1150
Magenta Magenta dye MF-1 100
filter High-boiling organic solvent (2) 100
Zinc hydroxide 2030
Cyan color- Lime-processed gelatin 1000
forming Emulsion 4R-1 996 9231
layer (high- (in terms of silver)
sensitivity Nitrogen-containing compound N-3 0.78 3
layer) Nitrogen-containing compound N-25 0.85 2.8
Zinc hydroxide .multidot. 6H.sub.2 O 5.64 19
Cyan coupler CC-1 189
Developing agent (3) 145
Developing agent (2) 18.5
Surfactant (1) 15
High-boiling organic solvent (1) 141
Water-soluble polymer (1) 3
Cyan color- Lime-processed gelatin 292
forming layer Emulsion 6R-1 391 3624
(medium- (in terms of silver)
sensitivity Nitrogen-containing compound N-3 2.04 7.8
layer) Nitrogen-containing compound N-25 0.59 1.95
Zinc hydroxide .multidot. 6H.sub.2 O 5.05 17
Cyan coupler CC-1 90
Developing agent (3) 69
Developing agent (2) 8.8
Surfactant (1) 7
High-boiling organic solvent (1) 67.3
Water-soluble polymer (1) 5
Cyan color- Lime-processed gelatin 730
forming layer Emulsion 6R-2 321 2975
(low- (in terms of silver)
sensitivity Nitrogen-containing compound N-3 3.34 12.8
layer) Nitrogen-containing compound N-25 0.76 2.5
Zinc hydroxide .multidot. 6H.sub.2 O 8.02 27
Cyan coupler CC-1 232
Developing agent (1) 178
Developing agent (2) 23
Surfactant (1) 17
High-boiling organic solvent (1) 173
Water-soluble polymer (1) 8
Interlayer Lime-processed gelatin 240
Antihalation Cyan dye CF-1 200
High-boiling organic solvent (2) 150
Subbing layer
PEN base (92 .mu.m)
Subbing Layer
Antistatic layer
Magnetic recording layer
Slipping layer
__________________________________________________________________________
Total amount of nitrogencontaining heterocyclic compound 180.65
.mu.mol/m.sup.2
Total amount of zinc ion 431 .mu.mol/m.sup.2
(those included in base emulsion) 33 .mu.mol/m.sup.2
Zinc ion/nitrogencontaining heterocyclic compound 2.38
Exposure of the light-sensitive material was carried out in the same manner
as in Example 1, except that the BPN42 filter used at the time of the
exposure was removed. Warm water at 40.degree. C. was applied to each of
the exposed light-sensitive materials, in an amount of 20 ml/m.sup.2 ; the
film surfaces of the light-sensitive material and the processing material
P-4 were overlapped with each other; they were heat-developed at
87.degree. C. for 20 sec using a heat drum. Further, the film surfaces of
the light-sensitive material and the processing material P-2 were
overlapped with each other, and they were processed for 20 seconds at a
temperature of 50.degree. C. using a heat drum. The processing material
P-4 was prepared in the same manner as for P-1, except that the amount of
guanidine picolinate was changed to 4500 mg/m.sup.2.
With respect to an image on the thus-processed light-sensitive material,
the transmission densities of wedge-like image with yellow, magenta, and
cyan colors were respectively measured by using a blue, green, and red
filter, to obtain characteristic curve, and the sensitivity and minimum
color density Dmin were obtained. The results are shown in Table 10. Each
of the blue, green, and red sensitivity was represented by a relative
value by assuming the value obtained by heat-development of sample 601 as
being 100.
TABLE 10
__________________________________________________________________________
Zn.sup.2+ /nitrogen
containing-
heterocyclic
compound Heat-development CN-16
(molar ratio)
Sensitivity
Dmin
Sensitivity
Dmin
__________________________________________________________________________
601 (This invention)
2.38 B 100 0.98
102 0.70
G 100 0.60 97 1.21
R 100 0.50 95 1.10
602 (Comparative example) 0.18 B 98 0.97 65 0.72
G 101 0.56 63 1.16
R 102 0.51 58 1.06
__________________________________________________________________________
From these results, it is understood that, even with the multilayer
light-sensitive material, high sensitivity and low Dmin were attained in
both heat-development and the CN-16 processing, when the divalent metal
cation for use in the present invention, which is an acid having
intermediate hardness/softness in accordance with the HSAB principle,
existed in amounts equimolar or more to the nitrogen-containing
heterocyclic compound for use in the present invention.
Samples were prepared by putting the multi-coated sample 601 into
cartridges, and the samples were loaded on a camera, and a photographing
test was carried out. The thus-photographed films were processed by one of
two kinds of processing methods, heat-development or CN-16 processing; and
in both cases, excellent images were obtained. When the images were
captured by Frontier (trade name), manufactured by Fuji Photo Film Co.,
Ltd., and then the images were outputted by PICTROGRAPHY 3000 (trade
name), excellent hard copies were obtained as well.
Having described our invention as related to the present embodiments, it is
our intention that the invention not be limited by any of the details of
the description, unless otherwise specified, but rather be construed
broadly within its spirit and scope as set out in the accompanying claims.
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